Physiological changes in green and red cherry tomatoes after photocatalytic ethylene degradation using continuous air flux.

In this work photocatalytic ethylene degradation (TiO2-UV) was applied in green cherry tomatoes with the aim to control biochemical and physiological changes during ripening. Photocatalytic process was performed at 18 °C ± 2 °C and 85% HR for 10 days using continuous air flux. Ethylene, O2 and CO2 concentration from cherry tomatoes under TiO2-UV and control (c) fruits, were measured by GC-MS for 10 days. After that, the tomatoes were stored for 20 days. During the photocatalysis process, ethylene was completely degraded and control fruits, the ethylene was 28.73 nL/g. Respiration rate was lower for fruits under TiO2-UV than control. During storage period, cherry tomatoes treated by TiO2-UV, showed lower ethylene concentration, respiration rate, total soluble solid, lycopene, sugar and organic acid content than control showing that the fruits treated with photocatalysis did not reach the full maturity. In addition, all the cherry tomatoes showed different maturity stages. Fungal incidence was higher in control fruits than fruits treated with photocatalysis. This research showed for the first time that photocatalytic technology preserved the physiological quality of cherry tomatoes for 30 days of storage, being a promised technology to preserve cherries tomatoes.

Peroxidation and photo-peroxidation of pantoprazole in aqueous solution using silver molybdate as catalyst.

In this study, silver molybdate was used as a catalyst in different oxidation processes to degrade pantoprazole (PAN) from aqueous suspension. The catalyst was synthesized using a controlled precipitation method and characterized by XRD, FTIR spectroscopy, BET analysis, Zeta potential, FEG-SEM/EDS, DRS and EPR. The α- and ß-phases of Ag2MoO4 were identified as crystalline structure of the butterfly-shaped particles. The metastable α-phase could be completely converted into ß-Ag2MoO4 by thermal treatment at 300 °C. The band gap energy of ß-Ag2MoO4 (Eg = 3.25 eV) is slightly higher than for as-prepared catalyst (α-Ag2MoO4 + ß-Ag2MoO4) (Eg = 3.09 eV), suggesting that as-prepared catalyst should be active under visible light. PAN is sensible to UV light irradiation, and the addition of H2O2 as electron acceptor enhanced the mineralization rate. In the catalytic UV-based reactions, high PAN oxidation efficiencies were obtained (>85%) but with low mineralization (32-64%). Catalytic peroxidation and photo-catalytic peroxidation under visible light showed the highest PAN oxidation efficiency, leading to its almost complete mineralization (>95%), even under dark conditions (98% in 120 min). Several degradation byproducts were identified and three mechanistic routes of PAN decomposition were proposed. The identified byproducts are less toxic than the parent compound. EPR coupled with the spin trapping method identified •OH radicals as the main ROS species in both photocatalytic and catalytic peroxidation reactions. Ag2MoO4 showed to be a promising catalyst to promote the decomposition of hydrogen peroxide into ROS.1.

1,4-Dioxane removal from water and membrane fouling elimination using CuO-coated ceramic membrane coupled with ozone.

1,4-Dioxane is a synthetic cyclic ether traditionally used as a chlorinated solvent stabilizer. It is a small molecule and recalcitrant compound that is difficult to remove by conventional processes and in this regard, there is a need for the development of new technologies. In this study, an innovative CuO-coated ceramic membrane (CM) reactor system that can be used to oxidize 1,4-dioxane dissolved in surface water by catalytic ozonation was developed. The effect of the thickness of the CuO deposited on the ceramic membrane surface on the permeability, fouling resistance, 1,4-dioxane removal, and toxicity was evaluated. The efficiency of the hybrid ozonation coupled to the use of a CuO-coated CM in 1,4-dioxane removal and the antifouling properties were assessed from TOC and 1,4-dioxane removal kinetics data. Reusability in four cycles was also tested. The performance of the CuO-coated CM remained stable during the four cycles of the reusability test. The ceramic membrane coated with CuO particles coupled with ozonation is appropriate for 1,4-dioxane degradation in the aqueous phase (45% efficiency, rate constant increased by a factor of 2.98 compared with the uncoated-hybrid process) and fouling removal (60 min to recovery the permeate flux).

Photocatalytic effect of addition of TiO2 to acrylic-based paint for passive toluene degradation.

Volatile organic compounds (VOCs) are known to be hazardous and associated with several human health problems. Thus, many technologies have been developed in recent years for their removal, such as thermal catalysis, photocatalysis and ozonization. In this study, the main objective was to evaluate the effects of incorporating titanium dioxide into an acrylic-based paint for gaseous toluene abatement. Paints with photocatalytic properties were prepared by adding TiO2 P25 powder to an acrylic-based paint, using the following proportions: 0, 10, 15, 20 and 50 wt% (dry basis). Toluene and CO2 concentrations at the reactor input and output were determined using GC/MS, and GC/FID, respectively, and the toluene conversion and CO2 formation were assessed. The compounds adsorbed onto photocatalytic paints were extracted and then identified by GC/MS. The results indicated that the addition of 50 wt% of TiO2 P25 results in a paint of reduced quality. The addition of 20 wt% of TiO2 P25 to the paint led to higher values for the photocatalytic conversion of toluene to CO2. The occurrence of two simultaneous processes was observed: the photocatalytic oxidation of toluene to CO2 and the self-degradation of the organic compounds, such as polymeric acrylic, in the paint. The adsorption of different compounds onto the photocatalytic paints was identified by GC/MS analysis. The use of photocatalytic paints is a promising technique for toluene abatement, but it requires further study and improvement particularly with regard to the effects of the self-degradation of the paint.

Photocatalytic degradation of polyvinylpyrrolidone in aqueous solution using TiO2/H2O2/UV system.

The photocatalytic degradation of high molecular weight polyvinylpyrrolidone (PVP), a water-soluble polymer, using a TiO2/H2O2/UV system was studied in an annular photoreactor using a mercury vapor lamp (125 W) as the radiation source. The effect of the initial hydrogen peroxide concentration and the operating conditions, such as initial concentration of PVP, photocatalyst dosage and initial pH, on the reaction rate was also evaluated. It was observed that the efficiency of the TiO2/H2O2/UV system was 33% higher than that of a system without H2O2, reaching total organic carbon removals of above 80% in 6 h of reaction, depending on the experimental conditions. The optimal photocatalyst dosage was found to be 0.50 g L-1. Also, the results demonstrate that the reaction rate increases as the pH and initial concentration of PVP decrease. This treatment can be carried out successfully under optimal conditions and enhance the biodegradability of the organic matter remaining at the end of the application of the TiO2/H2O2/UV system, as assessed by biochemical oxygen demand/chemical oxygen demand measurements.

Residue-based iron oxide catalyst for the degradation of simulated petrochemical wastewater via heterogeneous photo-Fenton process.

Iron oxide with a high degree of purity was recovered from waste and used as an environmentally friendly, low-cost catalyst in the application of the photo-Fenton process to simulated petrochemical wastewater (SPW). Iron oxide nanoparticles were characterized by X-ray powder diffraction, transmission electron microscopy, N2 adsorption/desorption isotherms, zeta potential, toxicity and atomic absorption spectrometry. The experiments were performed in a batch photochemical reactor, at 20 ± 2.0°C and pH 3.0. The SPW was efficiently mineralized and oxidized using a low catalyst dosage. The results showed that the organic compounds present in the wastewater were not adsorbed onto the solid surface. The solid was found to be stable with negligible leaching and low toxicity. The kTOC/kCOD ratios were calculated and varied according to the process: for a homogeneous reaction, the ratio obtained was 0.31 and for the heterogenous photo-Fenton process, it was closer to 1. The chemical oxygen demand and total organic carbon removal values were very close, indicating that the SPW is immediately mineralized, without producing partially oxidized compounds. The residue-based goethite studied represents a good alternative to commercially available catalysts in terms of sources and availability.

Combustion of pistachio shell: physicochemical characterization and evaluation of kinetic parameters.

The study of different renewable energy sources has been intensifying due to the current climate changes; therefore, the present work had the objective to characterize physicochemically the pistachio shell waste and evaluate kinetic parameters of its combustion. The pistachio shell was characterized through proximate analysis, ultimate analysis, SEM, and FTIR. The thermal and kinetic behaviors were evaluated by a thermogravimetric analyzer under oxidant atmosphere between room temperature and 1000 °C, in which the process was performed in three different heating rates (20, 30, and 40 °C min-1). The combustion of the pistachio shell presented two regions in the derivative thermogravimetric curves, where the first represents the devolatilization of volatile matter compounds and the second one is associated to the biochar oxidation. These zones were considered for the evaluation of the kinetic parameters E a , A, and f(α) by the modified method of Coats-Redfern, compensation effect, and master plot, respectively. The kinetic parameters for zone 1 were E a1 = 84.11 kJ mol-1, A 1 = 6.39 × 106 min-1, and f(α)1 = 3(1 - α)2/3, while for zone 2, the kinetic parameters were E a2 = 37.47 kJ mol-1, A 2 = 57.14 min-1, and f(α)2 = 2(1 - α)1/2.

Bio-syngas production from agro-industrial biomass residues by steam gasification.

This study evaluated the steam gasification potential of three residues from Brazilian agro-industry by assessing their reaction kinetics and syngas production at temperatures from 650 to 850°C and a steam partial pressure range of 0.05 to 0.3bar. The transition temperature between kinetic control and diffusion control regimes was identified. Prior to the gasification tests, the raw biomasses, namely apple pomace, spent coffee grounds and sawdust, were pyrolyzed in a fixed-bed quartz tubular reactor under controlled conditions. Gasification tests were performed isothermally in a magnetic suspension thermobalance and the reaction products were analyzed by a gas chromatograph with TCD/FID detectors. According to the characterization results, the samples presented higher carbon and lower volatile matter contents than the biomasses. Nevertheless, all of the materials had high calorific value. Syngas production was influenced by both temperature and steam partial pressure. Higher concentrations of H2 and CO were found in the conversion range of 50-80% and higher concentrations of CO2 in conversions around 10%, for all the gasified biochars. The H2/CO decreased with increasing temperature, mainly in kinetic control regime, in the lower temperature range. The results indicate the gasification potential of Brazilian biomass residues and are an initial and important step in the development of gasification processes in Brazil.

Recovery of iron oxides from acid mine drainage and their application as adsorbent or catalyst.

Iron oxide particles recovered from acid mine drainage represent a potential low-cost feedstock to replace reagent-grade chemicals in the production of goethite, ferrihydrite or magnetite with relatively high purity. Also, the properties of iron oxides recovered from acid mine drainage mean that they can be exploited as catalysts and/or adsorbents to remove azo dyes from aqueous solutions. The main aim of this study was to recover iron oxides with relatively high purity from acid mine drainage to act as a catalyst in the oxidation of dye through a Fenton-like mechanism or as an adsorbent to remove dyes from an aqueous solution. Iron oxides (goethite) were recovered from acid mine drainage through a sequential precipitation method. Thermal treatment at temperatures higher than 300 °C produces hematite through a decrease in the BET area and an increase in the point of zero charge. In the absence of hydrogen peroxide, the solids adsorbed the textile dye Procion Red H-E7B according to the Langmuir model, and the maximum amount adsorbed decreased as the temperature of the thermal treatment increased. The decomposition kinetics of hydrogen peroxide is dependent on the H(2)O(2) concentration and iron oxides dosage, but the second-order rate constant normalized to the BET surface area is similar to that for different iron oxides tested in this and others studies. These results indicate that acid mine drainage could be used as a source material for the production of iron oxide catalysts/adsorbents, with comparable quality to those produced using analytical-grade reagents.

Advanced oxidation processes applied to tannery wastewater containing Direct Black 38--elimination and degradation kinetics.

The application of advanced oxidation processes (H(2)O(2)/UV, TiO(2)/H(2)O(2)/UV and TiO(2)/UV) to treat tannery wastewater was investigated. The experiments were performed in batch and continuous UV reactors, using TiO(2) as a catalyst. The effect of the hydrogen peroxide concentration on the degradation kinetics was evaluated in the concentration range 0-1800 mg L(-1). We observed that the degradation rate increased as the hydrogen peroxide increased, but excessive H(2)O(2) concentration was detrimental because it acted as a hydroxyl radical scavenger since it can compete for the active sites of the TiO(2). In the H(2)O(2)/UV treatment, the COD removal reached around 60% in 4 h of reaction, indicating that the principal pollutants were chemically degraded as demonstrated by the results for BOD, COD, nitrate, ammonium and analysis of the absorbance at 254 nm. Artemia salina toxicity testing performed in parallel showed an increase in toxicity after AOP treatment of the tannery wastewater.

Evaluation of relative photonic efficiency in heterogeneous photocatalytic reactors.

The evaluation of photonic efficiency in heterogeneous photocatalysis remains elusive because the number of absorbed photons is difficult to assess experimentally. The photonic efficiency of heterogeneous photocatalytic reactors depends on the reactor geometry, irradiation source, and photocatalyst properties. In this work, the relative photonic efficiency of heterogeneous photocatalytic reactors to degrade an azo dye was evaluated using phenol as the standard system. The experimental tests were carried out in a batch reactor under different conditions of pH, catalyst dosage, initial concentration, and ultraviolet (UV) lamps. The kinetics of disappearance of both phenol and azo dye were studied using the initial rate method and were described according to the Langmuir-Hinshelwood (L-H) kinetic model. It was observed that the relative photonic efficiency depends on the adsorption/desorption properties of the photocatalyst.