MODELING REACTIVE GAS UPTAKE, TRANSPORT, AND TRANSFORMATION IN AGGREGATED SOILS

Gas diffusion research in soils covers, to a large extent, the transport behavior of practically insoluble gases. We extend the mathematical description of gas transport to include reactive gaseous components that hydrolyze in water such as SO2 and CO2. The path between the free atmosphere and the microporous niches is modeled by assuming penetration through gas-filled macropores, air-water phase transfer, and diffusion and speciation in the liquid phase. For hydrolyzable gases, the rate of mass transfer into and the total absorption capacity of the soil solution may be high. Both the capacity and the transfer rate are influenced by the soil-solution pH; for high pH, they become extremely high for SO2. The soil absorption of such gases is also influenced by soil structure. Well-aerated, near-neutral soils are a potentially important sink for SO2.

Heterogeneous model for gas transport in carbon molecular sieves

A dual resistance model with distribution of either barrier or pore diffusional activation energy is proposed in this work for gas transport in carbon molecular sieve (CMS) micropores. This is a novel approach in which the equilibrium is homogeneous, but the kinetics is heterogeneous. The model seems to provide a possible explanation for the concentration dependence of the thermodynamically corrected barrier and pore diffusion coefficients observed in previous studies from this laboratory on gas diffusion in CMS.(1.2) The energy distribution is assumed to follow the gamma distribution function. It is shown that the energy distribution model can fully capture the behavior described by the empirical model established in earlier studies to account for the concentration dependence of thermodynamically corrected barrier and pore diffusion coefficients. A methodology is proposed for extracting energy distribution parameters, and it is further shown that the extracted energy distribution parameters can effectively predict integral uptake and column breakthrough profiles over a wide range of operating pressures.

Synthesis and catalytic activity of new cu-based catalytic systems for the enhanced electrochemical CO2 reduction

This Ph.D. thesis concerns the synthesis of nanostructured Cu-containing materials to be used as electrode modifiers for the CO2 electroreduction in aqueous phase and the evaluation of their catalytic performances. Inspired by the fascinating concept of the artificial photosynthesis-oriented systems, several catalytic layers were electrochemically loaded on carbonaceous gas diffusion membranes, i.e., 3D structures that allow the design of eco-friendly materials for applications in green carbon recycling processes. In particular, early studies on Cu(I-II)-Cu(0) nanostructured materials were carried out to produce films on 4 cm2 sized supports by means of a fast and low-cost electrochemical procedure. Besides, through a screening of potentials, it was possible to find out a selective value for the CH3COOH production at -0.4 V vs RHE with a maximum productivity (1h reaction), ensured by the presence of the Cu+/Cu0 active redox couple (0.31 mmol gcat-1 h-1). On the basis of these results, further optimisations of the electrocatalyst chemical composition were carried out with the aim of (i) facilitating the interaction with CO2, (ii) increasing the dispersion of the catalytic active phase, and (iii) enhancing the CH3COOH productivity. To this aim, novel electrocatalysts based on layered double hydroxides (LDHs) were optimised, having as a final goal the formation of a new Cu2O-Cu0 based electrocatalyst derived from electrochemically achieved CuMgAl LDHs, subjected to calcination and reduction processes. The as-obtained electrocatalysts were tested for the selective production of CH3COOH and unprecedented results were obtained with the pristine CuMgAl LDH (2.0 mmol gcat-1 h-1). Additional characterisations of such an electrocatalyst have highlighted the possibility to achieve a ternary LDH in intimate contact with Cu2O-Cu0 species starting from the electrochemical deposition. The presence of these species, along with an alkaline environment on the electrode surface, were essential to preserve the selectivity towards the desired product, as confirmed by further operando studies.

Development of nanostructured bioanodes containing dendrimers and dehydrogenases enzymes for application in ethanol biofuel cells

This paper describes the use of the electrostatic layer-by-layer (LbL) technique for the preparation of bioanodes with potential application in ethanol/O(2) biofuel cells. More specifically, the LbL technique was employed for immobilization of dehydrogenase enzymes and polyamidoamine (PAMAM) dendrimers onto carbon paper support. Both mono (anchoring only the enzyme alcohol dehydrogenase, ADH) and bienzymatic (anchoring both ADH and aldehyde dehydrogenase, AldDH) systems were tested. The amount of ADH deposited onto the Toray (R) paper was 95 ng cm(-2) per bilayer. Kinetic studies revealed that the LbL technique enables better control of enzyme disposition on the bioanode, as compared with the results obtained with the bioanodes prepared by the passive adsorption technique. The power density values achieved for the mono-enzymatic system as a function of the enzyme load ranged from 0.02 to 0.063 mW cm(-2) for the bioanode containing 36 ADH bilayers. The bioanodes containing a gas diffusion layer (GDL) displayed enhanced performance, but their mechanical stability must be improved. The bienzymatic system generated a power density of 0.12 mW cm(-2). In conclusion, the LbL technique is a very attractive approach for enzyme immobilization onto carbon platform, since it enables strict control of enzyme disposition on the bioanode surface with very low enzyme consumption. (C) 2010 Elsevier B.V. All rights reserved.

Acoplamento de cela de difusão gasosa a sistema de análise por injeção seqüencial visando a determinação espectrofotométrica de sulfeto

A new configuration for coupling a gas diffusion cell to a sequential injection system is presented. The matrix exchange is made without the need for additional rotary injection valves or peristaltic pumps, keeping the original mechanical components of the sequential injection apparatus: one syringe pump (or peristaltic pump) and one selection valve. The system was tested constructing analytical curves for sulfide exploring the formation of the methylene blue dye. The proposed method has a detection limit of 60 µg L-1 S2-, with a linear dynamic range between 0.10 and 4.0 mg L-1 S2- concentrations, with a sampling frequency of 20 h-1.

Eletrocatálise das reações de oxidação de hidrogênio e de redução de oxigênio

This work discusses the electrocatalytic processes taking place in the polymer electrolyte fuel cell electrodes, specifically the hydrogen oxidation reaction (HOR) and the oxygen reduction reaction (ORR), because these are clear examples of electrochemical reactions favored by the use of electrocatalysts. Since the gaseous reactants are very little soluble in the electrolyte, the use of special electrodes, named gas diffusion electrodes, is required to promote easy and continuous access of reactant gases to the electrocatalytic sites. Besides this, other important aspects such as the use of spectroscopic techniques and of theoretical models to improve the knowledge of the electrocatalytic systems are shortly discussed.

Influência de M/C (M = Mo, Cu, Fe e W) incorporado à camada difusora do eletrodo de difusão de gás frente à reação de oxidação de hidrogênio na presença de CO

The performance of proton exchange membrane fuel cells (PEMFC) with Pt-based anodes is drastically lowered when CO-containing hydrogen is used to feed the system, because of the strong adsorption of CO on platinum. In the present work the effects of the presence of a conversion layer of CO to CO2 composed by several M/C materials (where M = Mo, Cu, Fe and W) in gas diffusion anodes formed by Pt catalysts were investigated. The diffusion layers formed by Mo/C e W/C show good CO-tolerance, and this was attributed to the CO removal by parallel occurrence of the water-gas shift reaction and the so-called bifunctional mechanism.

Sistema multicomutado de análise em fluxo para determinação de amônio e monocloramina em águas residuais e produtos de desinfecção

A binary sampling flow analysis system equipped with gas diffusion cell was developed for NH4+ and/or NH2Cl determination in wastewater and disinfection products samples based on the Berthelot reaction of the NH2Cl diffused through the semi-permeable PTFE membrane. The effect of the analytical conditions related to the reaction and flow parameters were evaluated and N-NH4+ and N-NH2Cl were determined in concentration ranges from 0.17 to 5 mg L-1 and from 0.5 to 14.5 mg L-1, respectively. Limits of detection (3σ) of 50 and 140 µg L-1 for N-NH4+ and N-NH2Cl were calculated, respectively, and RSD of 5 and 2% were calculated for 10 consecutive determinations of N-NH4+ (1 and 3 mg L-1) and N-NH2Cl (3 and 9 mg L-1), respectively with 30 determinations h-1.

A green flow-based procedure for fluorimetric determination of acid-dissociable cyanide in natural waters exploiting multicommutation

A flow system designed with solenoid valves is proposed for determination of weak acid dissociable cyanide, based on the reaction with o-phthalaldehyde (OPA) and glycine yielding a highly fluorescent isoindole derivative. The proposed procedure minimizes the main drawbacks related to the reference batch procedure, based on reaction with barbituric acid and pyridine followed by spectrophotometric detection, i.e., use of toxic reagents, high reagent consumption and waste generation, low sampling rate, and poor sensitivity. Retention of the sample zone was exploited to increase the conversion rate of the analyte with minimized sample dispersion. Linear response (r=0.999) was observed for cyanide concentrations in the range 1-200 mu g L(-1), with a detection limit (99.7% confidence level) of 0.5 mu g L(-1)(19 nmol L(-1)). The sampling rate and coefficient of variation (n=10) were estimated as 22 measurements per hour and 1.4%, respectively. The results of determination of weak acid dissociable cyanide in natural water samples were in agreement with those achieved by the batch reference procedure at the 95% confidence level. Additionally to the improvement in the analytical features in comparison with those of the flow system with continuous reagent addition (sensitivity and sampling rate 90 and 83% higher, respectively), the consumption of OPA was 230-fold lower.

Ethanol oxidation reaction on PtCeO(2)/C electrocatalysts prepared by the polymeric precursor method

This paper presents a study of the electrocatalysis of ethanol oxidation reactions in an acidic medium on Pt-CeO(2)/C (20 wt.% of Pt-CeO(2) on carbon XC-72R), prepared in different mass ratios by the polymeric precursor method. The mass ratios between Pt and CeO(2) (3:1, 2:1, 1:1, 1:2, 1:3) were confirmed by Energy Dispersive X-ray Analysis (EDAX). X-ray diffraction (XRD) structural characterization data shows that the Pt-CeO(2)/C catalysts are composed of nanosized polycrystalline non-alloyed deposits, from which reflections corresponding to the fcc (Pt) and fluorite (CeO(2)) structures were clearly observed. The mean crystallite sizes calculated from XRD data revealed that, independent of the mass ratio, a value close to 3 nm was obtained for the CeO(2) particles. For Pt, the mean crystallite sizes were dependent on the ratio of this metal in the catalysts. Low platinum ratios resulted in small crystallites. and high Pt proportions resulted in larger crystallites. The size distributions of the catalysts particles, determined by XRD, were confirmed by Transmission Electron Microscope (TEM) imaging. Cyclic voltammetry and chronoamperometic experiments were used to evaluate the electrocatalytic performance of the different materials. In all cases, except Pt-CeO(2)/C 1:1, the Pt-Ceo(2)/C catalysts exhibited improved performance when compared with Pt/C. The best result was obtained for the Pt-CeO(2)/C 1:3 catalyst, which gave better results than the Pt-Ru/C (Etek) catalyst. (C) 2009 Elsevier B.V. All rights reserved.

A Semi-Continuous Analyzer for the Fluorimetric Determination of Atmospheric Formaldehyde

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

NOISE GENERATED BY CAVITATION IN ORIFICE-PLATES WITH SOME GASEOUS EFFECTS.

An experimental investigation of the noise generated by cavitation in turbulent shear flows produced by confined sharp-edge orifice-plates is reported. The acoustic source strength of cavitation was determined by means of reciprocity type measurements. Experimentally determined scaling parameters are applied to a model to prototype scaling formula derived from dimensional analysis. The proposed formula is checked experimentally. Comparative photographic observations of the cavitation patterns for two different values of gas content are presented. The observed sound reduction, that occurs when supersaturated conditions exist downstream the orifice-plates, is explained by the effects of gas diffusion into the cavitation bubbles, and by simple acoustic attenuation.

Efeito de hipercabia no desenvolvimento de ovos de Trachemys scripta

Females of the painted turtle, Trachemys scripta, have an annual reproductive cycle. Their nest periods in Brazil starts around September and they lay about 7 - 10 eggs in nests dug in the soil. The eggs hatch in December. It is possible that the nest cover cause problems for the gas diffusion, also, the rain can wet or compact the soil covering the nest, or even soaked the whole area. Those problems may change the nests intern atmosphere decreasing O2 partial pressure (hypoxia) and increasing CO2 partial pressure (hypercarbia). The main objective of this study was to determine if and how hypercarbia (3% and 6%CO2), could influence the eggs and early posthatching development of the Trachemys scripta. We used three experimental groups of eggs incubated in: normal atmosphere (Control group CG, n = 14), hypercarbia with 3% of CO2 (G3%, n = 16) and with 6% of CO2 (G6%, n = 15). The profile of the mass increment during the egg development were not different among the groups, GC = 9.89±0.81g; G3% = 10.11±0.60g and G6% = 10.58±0.36g. In addition, the mass of the post-hatching turtles were the not different. There were not differences between the duration of the incubation period among the experimental groups, GC = 60.12±0.97days, G3% = 59.00±0.98days and G6% = 60.80±1.14days. The mortality rates were not affected by the hypercarbia, GC = 0.43 (43%), G3% = 0.27 (27%) and G6% = 0.37 (37%). Furthermore, the mass increment and the metabolic rate were the same among the early development of the turtles until 3 month after hatching. We conclude that hypercarbia (up to 6% of CO2) does not cause any alteration on the eggs or post-hatching normal development. It is possible that the combination of hypercarbia and hypoxia change those results

Formation and surface exchange of nitrous acid

Die salpetrige Säure (HONO) ist eine der reaktiven Stickstoffkomponenten der Atmosphäre und Pedosphäre. Die genauen Bildungswege von HONO, sowie der gegenseitige Austausch von HONO zwischen Atmosphäre und Pedosphäre sind noch nicht vollständig aufgedeckt. Bei der HONO-Photolyse entsteht das Hydroxylradikal (OH) und Stickstoffmonooxid (NO), was die Bedeutsamkeit von HONO für die atmosphärische Photochemie widerspiegelt.rnUm die genannte Bildung von HONO im Boden und dessen anschließenden Austausch mit der Atmosphäre zu untersuchen, wurden Messungen von Bodenproben mit dynamischen Kammern durchgeführt. Im Labor gemessene Emissionsflüsse von Wasser, NO und HONO zeigen, dass die Emission von HONO in vergleichbarem Umfang und im gleichen Bodenfeuchtebereich wie die für NO (von 6.5 bis 56.0 % WHC) stattfindet. Die Höhe der HONO-Emissionsflüsse bei neutralen bis basischen pH-Werten und die Aktivierungsenergie der HONO-Emissionsflüsse führen zu der Annahme, dass die mikrobielle Nitrifikation die Hauptquelle für die HONO-Emission darstellt. Inhibierungsexperimente mit einer Bodenprobe und die Messung einer Reinkultur von Nitrosomonas europaea bestärkten diese Theorie. Als Schlussfolgerung wurde das konzeptionelle Model der Bodenemission verschiedener Stickstoffkomponenten in Abhängigkeit von dem Wasserhaushalt des Bodens für HONO erweitert.rnIn einem weiteren Versuch wurde zum Spülen der dynamischen Kammer Luft mit erhöhtem Mischungsverhältnis von HONO verwendet. Die Messung einer hervorragend charakterisierten Bodenprobe zeigte bidirektionale Flüsse von HONO. Somit können Böden nicht nur als HONO-Quelle, sondern auch je nach Bedingungen als effektive Senke dienen. rnAußerdem konnte gezeigt werden, dass das Verhältnis von HONO- zu NO-Emissionen mit dem pH-Wert des Bodens korreliert. Grund könnte die erhöhte Reaktivität von HONO bei niedrigem pH-Wert und die längere Aufenthaltsdauer von HONO verursacht durch reduzierte Gasdiffusion im Bodenporenraum sein, da ein niedriger pH-Wert mit erhöhter Bodenfeuchte am Maximum der Emission einhergeht. Es konnte gezeigt werden, dass die effektive Diffusion von Gasen im Bodenporenraum und die effektive Diffusion von Ionen in der Bodenlösung die HONO-Produktion und den Austausch von HONO mit der Atmosphäre begrenzen. rnErgänzend zu den Messungen im Labor wurde HONO während der Messkampagne HUMPPA-COPEC 2010 im borealen Nadelwald simultan in der Höhe von 1 m über dem Boden und 2 bis 3 m über dem Blätterdach gemessen. Die Budgetberechnungen für HONO zeigen, dass für HONO sämtliche bekannte Quellen und Senken in Bezug auf die übermächtige HONO-Photolyserate tagsüber vernachlässigbar sind (< 20%). Weder Bodenemissionen von HONO, noch die Photolyse von an Oberflächen adsorbierter Salpetersäure können die fehlende Quelle erklären. Die lichtinduzierte Reduktion von Stickstoffdioxid (NO2) an Oberflächen konnte nicht ausgeschlossen werden. Es zeigte sich jedoch, dass die fehlende Quelle stärker mit der HONO-Photolyserate korreliert als mit der entsprechenden Photolysefrequenz, die proportional zur Photolysefrequenz von NO2 ist. Somit lässt sich schlussfolgern, dass entweder die Photolyserate von HONO überschätzt wird oder dass immer noch eine unbekannte, HONO-Quelle existiert, die mit der Photolyserate sehr stark korreliert. rn rn

Static and dynamic contact angle measurement on rough surfaces using sessile drop profile analysis with application to water management in low temperature fuel cells

Fuel Cells are a promising alternative energy technology. One of the biggest problems that exists in fuel cell is that of water management. A better understanding of wettability characteristics in the fuel cells is needed to alleviate the problem of water management. Contact angle data on gas diffusion layers (GDL) of the fuel cells can be used to characterize the wettability of GDL in fuel cells. A contact angle measurement program has been developed to measure the contact angle of sessile drops from drop images. Digitization of drop images induces pixel errors in the contact angle measurement process. The resulting uncertainty in contact angle measurement has been analyzed. An experimental apparatus has been developed for contact angle measurements at different temperature, with the feature to measure advancing and receding contact angles on gas diffusion layers of fuel cells.