Mass transport effects in the borohydride oxidation reaction-Influence of the residence time on the reaction onset and faradaic efficiency

The borohydride oxidation reaction (BOR) was studied on Pt and Au electrodes by cyclic voltammetry in dilute alkaline borohydride solutions (0.1 M NaOH + 10(-3) mol L(-1) NaBH(4)). More specifically, the electrodes were considered as either Vulcan XC72-supported Pt or Au (noted as Pt/C and Au/C, respectively) active layers or smooth Pt or Au surfaces, the latter possibly being covered by a layer of (non-metalized) Vulcan XC72 carbon powder. The BOR onset potential and the number of electrons (n(e-)) exchanged per BH(4)(-) anion (faradaic efficiency) were investigated for these electrodes, to determine whether the residence time of reaction intermediates (at the electrode surface or inside the porous layer) does influence the overall reaction pathway/completion. For the carbon-supported platinum, n(e-) strongly depends on the thickness of the active layer. While thin (ca. 0.5 mu m-thick) Pt/C active layers yield n(e-) < 4, thick layers (approximately 3 mu m) yield n(e-)approximate to 8, which can be ascribed to the sufficient residence time of the molecules formed within the active layer (H(2), by heterogeneous hydrolysis, or BOR intermediates) enabling further (near-complete) oxidation. This puts into evidence that not only the nature of the electrocatalyst is important to reach high BOR efficiency, but also the structure/thickness of the active layer. The same trend applies for Au/C active layers and for smooth Pt or Au surfaces covered with a layer of (inactive) Vulcan XC72. In addition, the BOR onset usually shifts negative when the reaction intermediates are trapped, which suggests that some of the intermediates are more easily oxidized than BH(4)(-) itself; based on literature data, BH(3)OH(-) species is a likely candidate. (C) 2011 Elsevier B.V. All rights reserved.

Human-animal interaction, stress, and embryo production in Bos indicus embryo donors under tropical conditions

This study investigated the effect of human-animal interaction (HAI) and the stress response on the quality of embryo production in superovulated Nelore (Bos indicus) cattle, under tropical conditions. Thirty-two females underwent a superovulation protocol for 5 days. Cortisol concentrations were determined in blood plasma collected on days 0, 4, and 5. Artificial insemination was performed on days 4 and 5, and nonsurgical embryo flushing on day 11. Embryo production and viability were determined. Human stimulation, animal behaviors, accidents, and handling time were recorded to assess HAI. Cattle age was negatively correlated with accidents, frequency of aversive behaviors, and negative stimuli by stockperson during transit through corral compartments to receive superovulation treatments. The factor analysis revealed two distinct groups. The first group was called stressed and had higher cortisol concentration than the nonstressed group, 16.0 +/- 2.1 and 12.5 +/- 1.0 ng/mL, respectively. Comparisons between these groups showed that the frequency of voice emissions by the stockperson and the number of accidents were higher in the stressed group, and also, the mean handling time was longer in the stressed group than for the nonstressed. As a result, viability rate of the embryos was 19% lower in the stressed group (P < 0.05). This indicates that intensive negative HAI is likely related to stress, which affects embryo production in a superovulation program.

Late Paleozoic-Early Triassic magmatism on the western margin of Gondwana: Collahuasi area, Northern Chile

The basement in the `Altiplano` high plateau of the Andes of northern Chile mostly consists of late Paleozoic to Early Triassic felsic igneous rocks (Collahuasi Group) that were emplaced and extruded along the western margin of the Gondwana supercontinent. This igneous Suite crops out in the Collalluasi area and forms the backbone of most of the high Andes from latitude 20 degrees to 22 degrees S. Rocks of the Collahuasi Group and correlative formations form art extensive belt of volcanic and subvolcanic rocks throughout the main Andes of Chile, the Frontal Cordillera of Argentina (Choiyoi Group or Choiyoi Granite-Rhyolite Province), and the Eastern Cordillera of Peru. Thirteen new SHRIMP U-Pb zircon ages from the Collahuasi area document a bimodal timing for magnatism, with a dominant peak at about 300 Ma and a less significant one at 244 Ma. Copper-Mo porphyry mineralization is related to the younger igneous event. Initial Hf isotopic ratios for the similar to 300 Ma zircons range from about -2 to +6 indicating that the magmas incorporated components with a significant crustal residence time. The 244 Ma magmas were derived from a less enriched source, with the initial HT values ranging from +2 to +6, suggestive of a mixture with a more depleted component. Limited whole rock (144)Nd/(143)Nd and (87)Sr/(86)Sr isotopic ratios further support the likelihood that the Collahuasi Group magmatism incorporated significant older crustal components, or at least a mixture of crustal sources with more and less evolved isotopic signatures. (C) 2007 International Association for Gondwana Research. Published by Elsevier B.V. All rights reserved.

Basic oxygen furnace slag as a treatment material for pathogens: Contribution of inactivation and attachment in virus attenuation

Basic oxygen furnace (BOF) slag media were studied as a potential treatment material in on-site sanitation systems. Batch and column studies were conducted to evaluate attenuation of the bacteriophage PR772 and 0.190 mu m diameter microspheres by BOF media, and to delineate the relative contributions of two principle processes of virus attenuation: inactivation and attachment. In the batch studies, conducted at 4 degrees C, substantial inactivation of PR772 did not occur in the pH 7.6 and 9.5 suspensions. At pH 11.4, bimodal inactivation of PR772 was observed, at an initial rate of 2.1 log C/C(0) day(-1) for the first two days, followed by a much slower rate of 0.124 log C/C(0) day(-1) over the following 10 days. Two column studies were conducted at 4 degrees C at a flow rate of 1 pore volume day(-1) using two slag sources (Stelco, Ontario; Tubarao, Brazil) combined with sand and pea gravel. In both column experiments, the effluent microsphere concentration approached input concentrations over time (reductions of 0.1-0.2 log C/C(0)), suggesting attachment processes for microspheres were negligible. Removal of PR772 virus was more pronounced both during the early stages of the experiments, but also after longer transport times (0.5-1.0 log C/C(0)). PR772 reduction appeared to be primarily as a result of virus inactivation in response to the elevated pH conditions generated by the BOF mixture (10.6-11.4). On-site sanitation systems using BOF media should be designed to maintain sufficient contact time between the BOF media and the wastewater to allow sufficient residence time of pathogens at elevated pH conditions. (C) 2009 Published by Elsevier Ltd.

Sequential injection analysis (SIA) and response surface methodology: A versatile small volume approach for optimization of photo-Fenton processes

Optimization of photo-Fenton degradation of copper phthalocyanine blue was achieved by response surface methodology (RSM) constructed with the aid of a sequential injection analysis (SIA) system coupled to a homemade photo-reactor. Highest degradation percentage was obtained at the following conditions [H(2)O(2)]/[phthalocyanine] = 7, [H(2)O(2)]/[FeSO(4)] = 10, pH = 2.5, and stopped flow time in the photo reactor = 30 s. The SIA system was designed to prepare a monosegment containing the reagents and sample, to pump it toward the photo-reactor for the specified time and send the products to a flow-through spectrophotometer for monitoring the color reduction of the dye. Changes in parameters such as reagent molar ratios. residence time and pH were made by modifications in the software commanding the SI system, without the need for physical reconfiguration of reagents around the selection valve. The proposed procedure and system fed the statistical program with degradation data for fast construction of response surface plots. After optimization, 97% of the dye was degraded. (C) 2009 Elsevier B.V. All rights reserved.

On the apparent lack of preferential site occupancy and electrooxidation of CO adsorbed at low coverage onto stepped platinum surfaces

We report time evolution studies of low coverage CO adsorption (surface hydrogen site blocking < 40%) and oxidative stripping on stepped Pt(776) and Pt(554) surfaces. It was observed that there is no preferential site occupancy for CO adsorption on step or terrace. It is proposed that CO adsorption onto these surfaces is a random process, and after CO adsorption there is no appreciable shift from CO-(111) to CO-(110) sites. This implies that after adsorption, CO molecules either have a very long residence time, or that the diffusion coefficient is much lower than previously thought. After CO electrooxidation the sites released included both terrace (111) and step (110) orientations. For surface hydrogen site blocking > 40%, the lateral interactions might play a role in the preferential CO site occupancy. (C) 2011 Elsevier B.V. All rights reserved.

Regression analysis of mean quality-adjusted survival time based on pseudo-observations

Regression models for the mean quality-adjusted survival time are specified from hazard functions of transitions between two states and the mean quality-adjusted survival time may be a complex function of covariates. We discuss a regression model for the mean quality-adjusted survival (QAS) time based on pseudo-observations, which has the advantage of directly modeling the effect of covariates in the QAS time. Both Monte Carlo Simulations and a real data set are studied. Copyright (C) 2009 John Wiley & Sons, Ltd.