Homogeneous photodegradation of CI Reactive Blue 4 using a photo-Fenton process under artificial and solar irradiation

The oxidation of C.I. Reactive Blue 4 (RB4) by photo-Fenton process mediated by lerrioxalate was investigated under artificial and solar irradiation. The RB4 degradation in acidic medium (pH 2.5) was evaluated by the decrease in Total Organic Carbon (TOC) content and color, measured by the decrease in chromophore absorption band (600 nm). The influence of ferrioxalate and H2O2 concentrations on the dye degradation was studied and best results were obtained using 1.0 mM ferrioxalate and 10 nM of hydrogen peroxide. Under these experimental conditions, 80% of TOC and 100% of color removal were obtained for a 0.1 mM RB4 dye in 35 min of solar irradiation. (c) 2006 Elsevier Ltd. All rights reserved.

A new shadow-ring device for measuring diffuse solar radiation at the surface

A new shadow-ring device for measuring diffuse solar radiation at the surface is presented. In this device the seasonal variation of shadow is followed by moving the detector horizontally. This unique characteristic facilitates its application for long and continuous periods of time. The blocking effect caused by the ring and other related geometric properties are formulated considering the diffuse solar radiation isotropic. The correction factor, shadow size, and ring-detector distance are derived as a function of radius and width of the ring, sun position, and local latitude. The largest blocking occurs during summer, when the ring-detector distance and the shadow width are the smallest, and it is compensated by a smaller blocking effect in the winter period. The performance of the new device is verified comparing daily values of diffuse solar radiation measured simultaneously with a similar device from Kipp & Zonen, Inc. The results show a very good agreement (within 2.5%) between both devices. The new device was also able to reproduce the radiometric properties of the local atmosphere based on 3-yr-long measurements of direct solar radiation using a pyrheliometer. The new device can be applied to estimate daily values of diffuse solar radiation at the surface in the range of 30degreesN-30degreesS with results comparable to other similar apparatuses.

Treatment of 1,10-phenanthroline laboratory wastewater using the solar photo-Fenton process

The red Fe2+-phenanthroline complex is the basis of a classical spectrophotometric method for determination of iron. Due to the toxicity of this complexing agent, direct disposal of the wastewaters generated in analytical laboratories is not environmentally safe. This work evaluates the use of the solar photo-Fenton process for the treatment of laboratory wastewaters containing phenanthroline. Firstly, the degradation of phenanthroline in water was evaluated at two concentration levels (0.1 and 0.01%, w/v) and the efficiencies of degradation using ferrioxalate (FeOx) and ferric nitrate were compared. The 0.01% w/v solution presented much higher mineralization, achieving 82% after 30 min of solar irradiation with both iron sources. The solar photo-Fenton treatment of laboratory wastewater containing, in addition to phenanthroline, other organic compounds such as herbicides and 4-chlorophenol, equivalent to 4500 mg L-1 total organic carbon (TOC) resulted in total degradation of phenanthroline and 25% TOC removal after 150 min, in the presence of either FeOx or ferric nitrate. A ratio of 1: 10 dilution of the residue increased mineralization in the presence of ferrioxalate, achieving 38% TOC removal after 120 min, while use of ferric nitrate resulted in only 6% mineralization over the same period. (c) 2007 Elsevier B.V. All rights reserved.

Influence of the iron source on the solar photo-Fenton degradation of different classes of organic compounds

In this work the influence of two different iron sources, Fe(NO3)(3) and complexed ferrioxalate (FeOx), on the degradation efficiency of 4-chlorophenol (4CP), malachite green, formaldehyde, dichloroacetic acid (DCA) and the commercial products of the herbicides diuron and tebuthiuron was studied. The oxidation of 4CP, DCA, diuron and tebuthiuron shows a strong dependence on the iron source. While the 4CP degradation is favored by the use of Fe(NO3)(3), the degradation of DCA and the herbicides diuron and tebuthiuron is most efficient when ferrioxalate is used. on the other hand, the degradation of malachite green and formaldehyde is not very influenced by the iron source showing only a slight improvement when ferrioxalate is used. In the case of formaldehyde, DCA, diuron and tebuthiuron, despite of the additional carbon introduced by the use of ferrioxalate, higher mineralization percentages were observed, confirming the beneficial effect of ferrioxalate on the degradation of these compounds. The degradation of tebuthiuron was studied in detail using a shallow pond type solar flow reactor of 4.5 L capacity and 4.5 cm solution depth. Solar irradiation of tebuthiuron at a flow rate of 9 L h(-1), in the presence of 10.0 mmol L-1 H2O2 and 1.0 mmol L-1 ferrioxalate resulted in complete conversion of this herbicide and 70% total organic carbon removal. (c) 2005 Elsevier Ltd. All rights reserved.

Dye-sensitized solar cell architecture based on indium-tin oxide nanowires coated with titanium dioxide

A new architecture for dye-sensitized solar cells is employed, based on a nanostructured transparent conducting oxide protruding from the substrate, covered with a separate active oxide layer. The objective is to decrease electron-hole recombination. The concept was tested by growing branched indium-tin oxide nanowires on glass using pulsed laser deposition followed by deposition of a sputtered titanium dioxide layer covering the wires. The separation of charge generation and charge transport functions opens many possibilities for dye-sensitized solar cell optimization. (c) 2007 Acta Materialia. Inc. Published by Elsevier Ltd. All rights reserved.

Degradation of tetracycline by photo-Fenton process - Solar irradiation and matrix effects

The degradation of the antibiotic tetracycline (TC) by the photo-Fenton process was evaluated under black-light and solar irradiation. The influences of iron source (Fe(NO3)(3) or ferrioxalate), hydrogen peroxide and matrix (pure water, surface water and a sewage treatment plant effluent-STP) were evaluated. Under black-light irradiation, TC degradation was favored in the presence of Fe(NO3)(3), achieving total degradation after 1 min irradiation, while under solar light the use of ferrioxalate favors the degradation. Nevertheless, no significant difference in total organic carbon removal was observed between these two iron sources, achieving a residual concentration of around 5 mg L-1 under black-light and 2 mg L-1 under solar light irradiation. No decrease of the degradation efficiency relative to pure water was observed when TC was irradiated in a sample of surface water, under either black-light or solar irradiation. However, lower efficiency was obtained under black-light when TC was present in a sample of STP effluent, indicating the interference of the constituents of this sample on the overall efficiency of the process. on the other hand, under solar irradiation in the presence of ferrioxalate, no influence of the matrix was observed, even in the sample of STP effluent, achieving total degradation of TC in 1.5 min. (c) 2006 Elsevier B.V. All rights reserved.

Modeling hourly diffuse solar-radiation in the city of São Paulo using a neural-network technique

dIn this work, a perceptron neural-network technique is applied to estimate hourly values of the diffuse solar-radiation at the surface in São Paulo City, Brazil, using as input the global solar-radiation and other meteorological parameters measured from 1998 to 2001. The neural-network verification was performed using the hourly measurements of diffuse solar-radiation obtained during the year 2002. The neural network was developed based on both feature determination and pattern selection techniques. It was found that the inclusion of the atmospheric long-wave radiation as input improves the neural-network performance. on the other hand traditional meteorological parameters, like air temperature and atmospheric pressure, are not as important as long-wave radiation which acts as a surrogate for cloud-cover information on the regional scale. An objective evaluation has shown that the diffuse solar-radiation is better reproduced by neural network synthetic series than by a correlation model. (C) 2004 Elsevier Ltd. All rights reserved.

Efficient Dye-Sensitized Solar Cells Based on the Combination of ZnO Nanorods and Microflowers

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Ga-Modified Nanostructured ZnO: Characterization and Application in Dye-Sensitized Solar Cells

ZnO has received great attention in many applications due to its electronic and optical properties. We report on the preparation of ZnO and gallium-containing ZnO (ZnO:Ga) nanoparticles by the precipitation method. The nanoparticles have the wurtzite structure and a high crystallinity. Gallium ions are present as Ga(3+), as evidenced by the binding energies through XPS. Porosity and surface area of the powder increased under increasing gallium level, explained by the smaller particle size of ZnO:Ga samples compared with ZnO. The estimated optical band gap of ZnO was 3.2 eV, comparable to ZnO:Ga.

Global and diffuse solar irradiances in urban and rural areas in southeast Brazil

The seasonal evolution of daily and hourly values of global and diffuse solar radiation at the surface are compared for the cities of São Paulo and Botucatu, both located in Southeast Brazil and representative of urban and rural areas, respectively. The comparisons are based on measurements of global and diffuse solar irradiance carried out at the surface during a six year simultaneous period in these two cities. Despite the similar latitude and altitude, the seasonal evolution of daily values indicate that São Paulo receives, during clear sky days, 7.8% less global irradiance in August and 5.1% less in June than Botucatu. on the other hand, São Paulo receives, during clear sky days, 3.6% more diffuse irradiance in August and 15.6% more in June than Botucatu. The seasonal variation of the diurnal cycle confirms these differences and indicates that they are more pronounced during the afternoon. The regional differences are related to the distance from the Atlantic Ocean, systematic penetration of the sea breeze and daytime evolution of the particulate matter in São Paulo. An important mechanism controlling the spatial distribution of solar radiation, on a regional scale, is the sea breeze penetration in São Paulo, bringing moisture and maritime aerosol that in turn further increases the solar radiation scattering due to pollution and further reduces the intensity of the direct component of solar radiation at the surface. Surprisingly, under clear sky conditions the atmospheric attenuation of solar radiation in Botucatu during winter - the biomass burning period due to the sugar cane harvest - is equivalent to that at São Paulo City, indicating that the contamination during sugar cane harvest in Southeast Brazil has a large impact in the solar radiation field at the surface.

Modeling hourly and daily fractions of UV, PAR and NIR to global solar radiation under various sky conditions at Botucatu, Brazil

In this analysis, using available hourly and daily radiometric data performed at Botucatu, Brazil, several empirical models relating ultraviolet (UV), photosynthetically active (PAR) and near infrared (NIR) solar global components with solar global radiation (G) are established. These models are developed and discussed through clearness index K(T) (ratio of the global-to-extraterrestrial solar radiation). Results obtained reveal that the proposed empirical models predict hourly and daily values accurately. Finally. the overall analysis carried Out demonstrates that the sky conditions are more important in developing correlation models between the UV component and the global solar radiation. The linear regression models derived to estimate PAR and NIR components may be obtained without sky condition considerations within a maximum variation of 8%. In the case of UV, not taking into consideration the sky condition may cause a discrepancy of up to 18% for hourly values and 15% for daily values. (C) 2008 Elsevier Ltd. All rights reserved.

Stepped light-induced transient measurements of photocurrent and voltage in dye-sensitized solar cells based on ZnO and ZnO:Ga

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Solar energy budgets in central Amazonian ecosystems: a comparison between natural forest and bare soil areas

In order to estimate the deforestation consequences on the actual solar energy budget of the Central Amazon Region, two ecosystems of different characteristics were compared. The present conditions of the region were represented by a typical 'terra firme' forest cover located at INPA's Ducke Forest Reserve, where the measurements necessary to evaluate its solar energy balance were carried out. The second ecosystem, simulating a deforested area, was represented by an area about 1.0 ha without natural vegetation and situated in the same Reserve. In this area lysimeters were placed, two of them filled with yellow latosol and two others with quartzose sand soil. Both soils are representative soils in the region. Their water balances were taken into account as well as the other parameters necessary to compute the solar energy balances. The results showed that water loss by evaporation was about 41.8% of the total precipitation in the yellow latosol lysimeters and about 26.4% for the quartzose sand ones. For the forest cover it was estimated an evapotranspiration of 67.9% of the rainfall amount. In relation to solar energy balance calculated for the forest cover, it was found that 83.1% of the total energy incoming to this ecosystem was used by the evapotranspiration process, while the remaining of 16.9% can be taken as sensible heat. For bare soils, 55.1% and 31.8% of the total energy were used as latent heat by yellow latosol and quartzose sand soils, respectively. So, the remaining amounts of 44.9% and 68.2% were related to sensible heat and available to atmospheric air heating of these ecosystems. Such results suggest that a large deforestation of the Amazon Region would have direct consequences on their water and solar radiation balances, with an expected change on the actual climatic conditions of the region. © 1993.

Influence of Earth's shadow on the rotational motion of an artificial satellite perturbed by solar radiation torque

A semi-analytical approach is proposed to study the rotational motion of an artificial satellite under the influence of the torque due to the solar radiation pressure and taking into account the influence of Earth's shadow. The Earth's shadow is introduced in the equations for the rotational motion as a function depending on the longitude of the Sun, on the ecliptic's obliquity and on the orbital parameters of the satellite. By mapping and computing this function, we can get the periods in which the satellite is not illuminated and the torque due to the solar radiation pressure is zero. When the satellite is illuminated, a known analytical solution is used to predict the satellite's attitude. This analytical solution is expressed in terms of Andoyer's variables and depends on the physical and geometrical properties of the satellite and on the direction of the Sun radiation flux. By simulating a hypothetical circular cylindrical type satellite, an example is exhibited and the results agree quite well when compared with a numerical integration. © 1997 COSPAR. Published by Elsevier Science Ltd.

Diurnal evolution of solar radiation at the surface in the city of São Paulo: Seasonal variation and modeling

Seasonal variations in the diurnal evolution of the global, diffuse and direct solar radiation at the surface, the clearness index, diffuse fraction and direct fraction are described in detail for the City of Sao Paulo, Brazil. The description is based on measurements of global and diffuse solar radiation carried out over 5.25 years. The diffuse component was measured with a shadow-band device. The annual evolution of the amplitude of the diurnal cycle of all radiometric parameters indicates a seasonal pattern with two distinct periods: autumn-winter and spring-summer. About 10% of the observed period was characterized by clear sky days. This seasonal variation is determined by a larger incidence of clear sky days in the autumn-winter period. Reductions of up to 10% in hourly and daily values of global radiation were observed in conjunction with an increase in particulate matter concentration on clear sky days. The pollution effect may be responsible for the discrepancy, of 16%, found between local and more regional estimates of global solar radiation in Sao Paulo. The diurnal evolution of hourly values of monthly-averaged global and diffuse solar radiation were successfully estimated by the empirical expressions derived here. Daily values of monthly-averaged global solar radiation were satisfactorily estimated using the Angstrom expression.