Erick R. Bandala

Solar photocatalytic degradation of Aldrin

Abstract Photocatalytic degradation of the pesticide Aldrin dissolved in water was carried out, in one case, using concentrated solar radiation and, in another case, using non-concentrated solar radiation. In these experiments, the effects of catalyst concentration, oxidant agent concentration, and solar irradiation were tested. In experiments without irradiation, strong adsorption of the pesticide over titanium dioxide was observed in the first few minutes of contact in the presence of titanium dioxide (TiO 2 ). These results can be explained by means of Coulombic interactions between the catalyst surface and the pesticide molecules. During the photodegradation process, results show a residual degradation (photolysis) in both the cases, when no catalyst was added. In the case of the non-concentrated solar system, the achieved results suggest that the use of H 2 O 2 increased the degradation rate. For concentrated sunlight, an increase of the Aldrin concentration was observed during the first few minutes of irradiation. This can be explained as a desorption process that is triggered by a change in surface charge of the catalyst in the presence of hydrogen peroxide (H 2 O 2 ) during irradiation. When photocatalysis was performed with TiO 2 alone, no Aldrin was detected in the water solutions throughout the entire experiment. This result was unexpected; however, it might be explained by the adsorption of the pesticide on the catalyst surface and by the absence of the oxidant’s effect. Three transformation products (TPs) of the degradation process were identified: dieldrin, chlordene and 12-hydroxy-dieldrin. The results presented here are in agreement with previously reported results for photocatalytic degradation of other chlorinated pesticides using lamps as radiation sources.

Degradation of 1-hydroxy-2,4-dinitrobenzene from aqueous solutions by electrochemical oxidation: role of anodic material.

Electrochemical oxidation (ECOx) of 1-hydroxy-2,4-dinitrobenzene (or 2,4-dinitrophenol: 2,4-DNP) in aqueous solutions by electrolysis under galvanostatic control was studied at Pb/PbO2, Ti/SnO2, Ti/IrxRuySnO2 and Si/BDD anodes as a function of current density applied. Oxidative degradation of 2,4-DNP has clearly shown that electrode material and the current density applied were important parameters to optimize the oxidation process. It was observed that 2,4-DNP was oxidized at few substrates to CO2 with different results, obtaining good removal efficiencies at Pb/PbO2, Ti/SnO2 and Si/BDD anodes. Trends in degradation way depend on the production of hydroxyl radicals (OH) on these anodic materials, as confirmed in this study. Furthermore, HPLC results suggested that two kinds of intermediates were generated, polyhydroxylated intermediates and carboxylic acids. The formation of these polyhydroxylated intermediates seems to be associated with the denitration step and substitution by OH radicals on aromatic rings, this being the first proposed step in the reaction mechanism. These compounds were successively oxidized, followed by the opening of aromatic rings and the formation of a series of carboxylic acids which were at the end oxidized into CO2 and H2O. On the basis of these information, a reaction scheme was proposed for each type of anode used for 2,4-D oxidation.

Chlorinated Pesticides (2,4-D and DDT) Biodegradation at High Concentrations Using Immobilized Pseudomonas Fluorescens

Abstract Degradation of two chlorinated pesticides (2,4-D and DDT) using a 54-mL glass column packed with tezontle (a low-cost basaltic scoria) was tested. Bacteria were cultured in YPG (yeast, peptone, and glucose) liquid medium at 32°C. The rich medium was pumped during 24 h through the column to inoculate it. Later, the wasted medium was discharged and the pesticide added. Optical densities, TOC, and pesticide concentration were determined. Pesticide removals for 2,4-D (with initial concentration between 100 and 500 mg/L) were about 99%. DDT removal (at initial concentration of up to 150 mg/L) was as high as 55–99%. TOC removals for 2,4-D was in the 36-87% interval, whereas for DDT they were as high as 36–78%.

Enhancing the electrochemical oxidation of acid-yellow 36 azo dye using boron-doped diamond electrodes by addition of ferrous ion

This work shows preliminary results on the electrochemical oxidation process (EOP) using boron-doped diamond (BDD) electrode for acidic yellow 36 oxidation, a common azo dye used in textile industry. The study is centred in the synergetic effect of ferrous ions and hydroxyl free radicals for improving discoloration of azo dye. The assays were carried out in a typical glass cell under potentiostatic conditions. On experimental conditions, the EOP was able to partially remove the dye from the reaction mixture. The reaction rate increased significantly by addition of Fe(2+) (1mM as ferrous sulphate) to the system and by (assumed) generation of ferrate ion [Fe(VI)] over BDD electrode. Ferrate is considered as a highly oxidizing reagent capable of removing the colorant from the reaction mixture, in synergistic action with the hydroxyl radicals produced on the BDD surface. Further increases in the Fe(2+) concentration lead to depletion of the reaction rate probably due to the hydroxyl radical scavenging effect of Fe(2+) excess in the system.

Decontamination of soil washing wastewater using solar driven advanced oxidation processes

Decontamination of soil washing wastewater was performed using two different solar driven advanced oxidation processes (AOPs): the photo-Fenton reaction and the cobalt/peroxymonosulfate/ultraviolet (Co/PMS/UV) process. Complete sodium dodecyl sulphate (SDS), the surfactant agent used to enhance soil washing process, degradation was achieved when the Co/PMS/UV process was used. In the case of photo-Fenton reaction, almost complete SDS degradation was achieved after the use of almost four times the actual energy amount required by the Co/PMS/UV process. Initial reaction rate in the first 15min (IR15) was determined for each process in order to compare them. Highest IR15 value was determined for the Co/PMS/UV process (0.011mmol/min) followed by the photo-Fenton reaction (0.0072mmol/min) and the dark Co/PMS and Fenton processes (IR15=0.002mmol/min in both cases). Organic matter depletion in the wastewater, as the sum of surfactant and total petroleum hydrocarbons present (measured as chemical oxygen demand, COD), was also determined for both solar driven processes. It was found that, for the case of COD, the highest removal (69%) was achieved when photo-Fenton reaction was used whereas Co/PMS/UV process yielded a slightly lower removal (51%). In both cases, organic matter removal achieved was over 50%, which can be consider proper for the coupling of the tested AOPs with conventional wastewater treatment processes such as biodegradation.

Comparison of Solar Collection Geometries for Application to Photocatalytic Degradation of Organic Contaminants

A comparative study between four different solar collectors was carried out using oxalic acid and the pesticide carbaryl as model contaminants. The comparison was performed by means of a figure-of-merit developed for solar driven Advanced Oxidation Technology systems by the International Union of Pure and Applied Chemistry (IUPAC) for standardization purposes. It was found that there is a relationship between the photocatalyst concentration and the overall solar collector performance. Compound parabolic concentrator was the geometry with the highest turnover rate in the photocatalytic process of oxalic acid, followed by the V trough collector, the parabolic concentrator, and, finally, the tubular collector. When a comparative analysis was carried out using the figure of merit (collector area per order, ACO), the parabolic trough concentrator (PTC) showed the highest efficiency (lower ACO values) at low photocatalyst loads. The V trough collector and the compound parabolic collector showed similar ACO values, which decreased as the photocatalyst concentration increased. The tubular collector was the worst in all catalyst concentration ranges, with the higher collection surface by the order of oxalic acid. Photocatalytic degradation of the carbamic pesticide was tested using the same experimental arrangement used for oxalic acid. In this case, the use of the figureof-merit allowed us to observe the same trend as that displayed for oxalic acid, but with slightly higher ACO values. Results of this work demonstrate that a comparison between different reactor geometries for photocatalytic processes is viable using this figure-ofmerit approach and that the generated results can be useful in the standardization of a methodology for solar driven processes comparison and provide important data for the scaling up of the process. DOI: 10.1115/1.2390986

Removal of Aldrin, Dieldrin, Heptachlor, and Heptachlor Epoxide Using Activated Carbon and/or Pseudomonas fluorescens Free Cell Cultures

Degradation of aldrin (1,2,3,4,10,10-Hexachloro-1,4,4a,5,8,8a-hexahydro-1,4:5-8-dimethanonaphthalene), heptachlor (1H-1,4,5,6,7,8,8-heptachloro-3a,4,7,7a-tetrahydro-4,7-methano indene), dieldrin (1aα,2β,2aα,3β,6β,6aα,7β,7aα)-3,4,5,6,9,9-Hexachloro-1a,2,2a,3,6,6a,7,7a-octahydro-2,7:3,6-d-methanonaphtha[2,3-b]oxirene, and heptachlor epoxide (1aα, 1bβ,2α,5α,5αβ,6β,6aα-2,3,4,5,6,7,7-Heptachloro-1a,1b,5,5a,6,6a-hexahydro-2,5-methano-2H-inden[1,2-b]-oxirene) was tested using free cultures of Pseudomonas fluorescens under controlled conditions. Pesticide concentrations were monitored by gas chromatography during 120 h. Percentages of degradation and biodegradation rates (BDR) were calculated. Data showed a trend suggesting a relation between chemical structure and degradability. Degradation kinetics for each pesticide tested showed that the highest degradation rates were found in the first 24 h. Kinetics data were adjusted to an empirical equation in order to predict their behavior, and the correlation coefficients obtained were satisfactory. Gas chromatography/mass spectrometry (GC/MS) analysis of the final extracts allowed the identification of chlordene and monodechlorodieldrin, which have been reported as final metabolite produced in the biodegradation of this kind of compounds. Regarding adsorption of pesticides on activated vegetal carbon, we concluded that removal efficiencies between 95.45 and 97.18% can be reached, depending on the pesticide and the carbon dose applied. The values for K from the Freundlich equation were quite similar for the four pesticides (between 1.0001 and 1.04), whereas the n values were quite different for each pesticide in the following order of affinity: dieldrin > aldrin > heptachlor epoxide > heptachlor. Equilibrium times, very important for scaling up the process, were between 43 min and 1 h, for the heptachlor epoxide and the heptachlor, respectively.

Radiation absorption and rate constants for carbaryl photocatalytic degradation in a solar collector

Abstract We discuss an analytical model for the evaluation of radiation absorption in a tubular photocatalytic reactor. The model has no adjustable parameters and takes into account scattering in all directions. We compare the results of this model with those of Monte Carlo (MC) simulations and of a Lambert–Beer (LB) approximation, for a reactor illuminated by a parabolic solar concentrator. A good correspondence is found with the MC simulations. In particular, the model displays the correct saturation behavior of absorption for large catalyst particle concentrations, which is not obtained with the LB approximation. We have carried out experiments for the degradation of carbaryl in a solar parabolic collector (PC). The model is used to calculate the rate constant for this degradation from the experimental data. The theoretical model predictions reproduce well, the trends observed in the experiments.

Inactivation of Ascaris eggs in water using sequential solar driven photo-Fenton and free chlorine

Sequential helminth egg inactivation using a solar driven advanced oxidation process (AOP) followed by chlorine was achieved. The photo-assisted Fenton process was tested alone under different H(2)O(2) and/or Fe(II) concentrations to assess its ability to inactivate Ascaris suum eggs. The effect of free chlorine alone was also tested. The lowest egg inactivation results were found using Fe(II) or H(2)O(2) separately (5 and 140 mmol L(-1), respectively) in dark conditions, which showed about 28% inactivation of helminth eggs. By combining Fe(II) and H(2)O(2) at the same concentrations described earlier, 55% of helminth egg inactivation was achieved. By increasing the reagents concentration two-fold, 83% egg inactivation was achieved after 120 min of reaction time. Process efficiency was enhanced by solar excitation. Using solar disinfection only, the A. suum eggs inactivation reached was the lowest observed (58% egg inactivation after 120 min (120 kJ L(-1))), compared with tests using the photo-Fenton process. The use of the photo-Fenton reaction enhanced the process up to over 99% of egg inactivation after 120 kJ L(-1) when the highest Fe(II) and H(2)O(2) concentration was tested. Practically no effect on the helminth eggs was observed with free chlorine alone after 550 mg min L(-1) was used. Egg inactivation in the range of 25-30% was obtained for sequential processes (AOP then chlorine) using about 150 mg min L(-1).

Deactivation of Highly Resistant Microorganisms in Water Using Solar Driven Photocatalytic Processes

Inactivation of Bacillus subtilis spores was carried out using solar-driven Advanced Oxidation Processes (AOPs) alone and coupled with free chlorine in sequential processes. Experimental results showed that Fenton-like processes are more efficient under the tested conditions than heterogeneous photocatalytic processes using suspended titanium dioxide. Experimental data were fitted using modified Chick-Watson kinetics and the accumulated energy as the radiation dose needed for spore deactivation. It was demonstrated that the deactivation of B. subtilis spores using chlorine can be enhanced by primary treatment with photocatalysis. This study also suggests that AOPs could be an effective alternative to control the occurrence of highly resistant waterborne pathogens.