Characterization of Cuban and Brazilian natural zeolites by photoacoustic spectroscopy and electron paramagnetic resonance.

This report describes the photoacoustic and electron paramagnetic resonance investigations of Brazilian and Cuban zeolites. Photoacoustic optical absorption measurements indicate the presence of iron (Fe3+) ions with their respective transition bands for both zeolites. Two species of manganese (Mn2+ and Mn3+) were identified in the Cuban sample and the electronic transitions assigned. Iron and manganese ions were confirmed through nonradiative relaxation (τ) and characteristic diffusion (τß) times evaluation, whose values were found to be τBRA = 5.40 ms, τCUB = 4.60 ms, τßBRA = 387 µs and τßCUB = 305 µs. Crystal field (Dq-BRA/Dq-CUB = 1048 cm-1/945 cm-1) plus Racah (B-BRA/B-CUB = 457 cm-1/813 cm-1 and C-BRA/C-CUB = 3655 cm-1/2496 cm-1) parameters were assessed as well. Paramagnetic resonance corroborated Fe3+ ions present in the Brazilian zeolite occupying sites showing axial and/or rhombic symmetry distortions. For the Cuban sample, results reveal the characteristic hyperfine sextet lines of Mn2+ overlapping the Fe3+ line. Values of Landé factor and isotropic hyperfine splitting constant were found to be 2.0 and 9.7 mT, respectively. This tells us that the Mn2+ lies in octahedral symmetry probably replacing calcium ions and point towards an ionic bonding character of the Mn2+ and its surroundings.

A sulfur hexafluoride sensor using quantum cascade and CO2 laser-based photoacoustic spectroscopy.

The increase in greenhouse gas emissions is a serious environmental problem and has stimulated the scientific community to pay attention to the need for detection and monitoring of gases released into the atmosphere. In this regard, the development of sensitive and selective gas sensors has been the subject of several research programs. An important greenhouse gas is sulphur hexafluoride, an almost non-reactive gas widely employed in industrial processes worldwide. Indeed it is estimated that it has a radiative forcing of 0.52 W/m(2). This work compares two photoacoustic spectrometers, one coupled to a CO(2) laser and another one coupled to a Quantum Cascade (QC) laser, for the detection of SF(6). The laser photoacoustic spectrometers described in this work have been developed for gas detection at small concentrations. Detection limits of 20 ppbv for CO(2) laser and 50 ppbv for quantum cascade laser were obtained.

Detection of greenhouse gas precursors from diesel engines using electrochemical and photoacoustic sensors.

Atmospheric pollution is one of the worst threats to modern society. The consequences derived from different forms of atmospheric pollution vary from the local to the global scale, with deep impacts on climate, environment and human health. Several gaseous pollutants, even when present in trace concentrations, play a fundamental role in important processes that occur in atmosphere. Phenomena such as global warming, photochemical smog formation, acid rain and the depletion of the stratospheric ozone layer are strongly related to the increased concentration of certain gaseous species in the atmosphere. The transport sector significantly produces atmospheric pollution, mainly when diesel oil is used as fuel. Therefore, new methodologies based on selective and sensitive gas detection schemes must be developed in order to detect and monitor pollutant gases from this source. In this work, CO(2) Laser Photoacoustic Spectroscopy was used to evaluate ethylene emissions and electrochemical analyzers were used to evaluate the emissions of CO, NO(x) and SO(2) from the exhaust of diesel powered vehicles (rural diesel with 5% of biodiesel, in this paper called only diesel) at different engine rotation speeds. Concentrations in the range 6 to 45 ppmV for ethylene, 109 to 1,231 ppmV for carbon monoxide, 75 to 868 ppmV for nitrogen oxides and 3 to 354 ppmV for sulfur dioxide were obtained. The results indicate that the detection techniques used were sufficiently selective and sensitive to detect the gaseous species mentioned above in the ppmV range.

Nutrient release by a Brazilian sedimentary zeolite

This report describes the characterization of a sedimentary occurrence from the Parnaíba Basin, Brazil, containing the zeolite stilbite intertwined with smectitic clay mineral. The head samples from different sites present a wide content range of the zeolitic phase - 15 percent to 50 percent. The use of simple separation techniques - conventional gravitic treatments - yields concentrates containing about 67 percent of the zeolitic component. Assays with the amendments of these concentrates with plant nutrients yield release rates matching those reported for similar commercial products.

São apresentadas as propriedades físico-químicas de uma ocorrência sedimentar da Bacia do Parnaíba, Brasil, da zeólita estilbita, agregada a uma argila esmectítica. As amostras de diferentes sítios apresentam uma ampla variação do mineral zeolítico: entre 15 por cento a 50 por cento. A utilização de espirais concentradoras foi suficiente para obtenção de concentrados contendo até 67 por cento do mineral. Ensaios laboratoriais do concentrado dopado com fertilizantes revelam taxas de liberação de nutrientes comparáveis aos obtidos com produtos comerciais similares.

Photothermal gas analyzer for simultaneous measurements of thermal diffusivity and thermal effusivity.

In this paper, we describe a new, simple, and fast photothermal method for simultaneous measurements of two important gas thermal properties: thermal diffusivity and thermal effusivity. The method consists essentially in combining a photoacoustic cell and a thermal wave pyroelectric cell enclosed in a single compact gas analyzer. The photoacoustic cell is kept filled with synthetic air and sealed. The pyroelectric cell is also filled with synthetic air, and after some warm up time, the synthetic air is exchanged to the gas of interest. It is shown that the analysis of the transient and saturation signals of both photoacoustic and pyroelectric cells is capable of measuring the thermal properties with an accuracy of 3%. This particular capability of performing simultaneously the measurements of thermal diffusivity and thermal effusivity allows us to carry on the complete characterization of the thermal properties of gases.

Ammonia detection by using quantum-cascade laser photoacoustic spectroscopy.

A pulsed quantum-cascade distributed-feedback laser, temperature tunable from -41 degrees C to +31.6 degrees C, and a resonant differential photoacoustic detector are used to measure trace-gas concentrations to as low as 66 parts per 10(9) by volume (ppbv) ammonia at a low laser power of 2 mW. Good agreement between the experimental spectrum and the simulated HITRAN spectrum of NH3 is found in the spectral range between 1046 and 1052 cm(-1). A detection limit of 30 ppbv ammonia at a signal-to-noise ratio of 1 was obtained with the quantum-cascade laser (QCL) photoacoustic (PA) setup. Concentration changes of approximately 50 ppbv were detectable with this compact and versatile QCL-based PA detection system. The performance of the PA detector, characterized by the product of the incident laser power and the minimum detectable absorption coefficient, was 4.7 x 10-9 W cm(-1).