RESUMO
Background: This work studied the use of the organic fertilizers DTPA-Fe and EDDS-Fe as iron chelates for solar driven photo-Fenton process at natural pH. This process was proposed to investigate its performance on removing a mixture of agrochemicals (propiconazole, imidacloprid and diuron) from pineapple processing wastewater to obtain a suitable effluent to be reused in the agricultural sector. Methods: Experiments were carried out in a solar simulator with a stirred cylindric photoreactor, with a volume of 150 mL and controlled temperature (20°C). The first set of experiments was carried out with ultrapure water to determine optimal iron and H 2O 2 concentrations. The second was performed with simulated wastewater of pineapple processing. Results: The optimized operational conditions for both iron complexes were 10 mg L -1 of Fe (III) and 25 mg L -1 of H 2O 2, since more than 80% of micropollutants (MP) (at an initial concentration of 1 mg L -1 of each compound) were removed in only 20 min with both DTPA-Fe and EDDS-Fe. The effect of organic matter and inorganic salts on radicals scavenging and chelates stability was also investigated in the experiments performed with synthetic pineapple processing wastewater. The results disclosed differences depending on the iron complex. Nitrites were the principal component influencing the tests carried out with EDDS-Fe. While carbonates at low concentration only significantly affected the experiments performed with DTPA-Fe, they were the major influence on the MPs removal efficiency decrease. In contrast, the presence of Ca 2+ and Mg 2+ only influence on this last one. Finally, the results of phytotoxicity disclosed the suitability of treated effluent to be reused in the agricultural sector. Conclusions: This work demonstrated that solar powered photo-Fenton catalysed by iron fertilizer EDDS is a suitable technology for depolluting water streams coming from pineapple processing plants at circumneutral pH, and its subsequent reuse for crop irrigation.
RESUMO
Background: The management of empty pesticide containers (EPC) in Bolivia has been recently promoted as a control strategy for dispersed pollution in surface and underground water bodies, as well as in soil. It comprises the rinsing and proper disposal or reuse of clean EPC. However, the rinsing transfers the hazard to water, which must be properly treated before being discharged. Methods: In this study, solar photo-Fenton at low Fe 2+ doses were tested at pilot plant scale in Cochabamba (Bolivia) for the removal of pesticides dimethoate and atrazine in their commercial form, spiked in river water. Results: The results demonstrated that solar photo-Fenton ([H 2O 2] 0 = 200 mg L -1) with Fe 2+ concentrations between 0.5 and 1.5 mg L -1 is an effective method to remove dimethoate and atrazine, at an initial concentration of 10 mg L -1 each. Efficiency increased when increasing Fe 2+ doses, achieving a removal over 99% of both pesticides after a solar irradiation period of 60 minutes (corresponding to an accumulated energy of 4.96 kJ L -1). Conclusions: The presence of high concentrations of natural components of river water, mainly organic and inorganic carbon species, would have contributed to hydroxyl radical scavenging, explaining, together with the low iron dose applied, the high energy (irradiation time) and high hydrogen peroxide concentration required to produce pesticide depletion. Additionally, the relatively low oxidant consumption and mineralization observed leave room for process optimization regarding oxidant and catalyst doses and warrant further studies on its coupling with biological or other post-treatments for the removal of transformation products.
RESUMO
Dichlorvos (DDVP) is an organophosphorus pesticide that has been classified as highly hazardous chemical by the World Health organization. In this study, the fate of the pesticide DDVP in natural water compartments was examined under simulated sunlight. Moreover, the effect of UV-254 irradiation on DDVP depletion was also studied. In deionized water, DDVP was photodegraded only in the presence of dissolved molecular oxygen. The photodegradation during the first 6â¯h of sunlight irradiation occurred with pseudo first-order kinetics, and the rate constants were 0.040â¯h-1 at pHâ¯7 and 0.064â¯h-1 at pHâ¯3. A reaction mechanism for the generation of reactive oxygen species (ROS) via DDVP photoabsorption was proposed. Humic acids (HA) played a double role as photosensitizer and inhibitor, observing an enhancement on DDVP photodegradation at low HA concentration (TOCâ¯=â¯2â¯mgâ¯L-1). The depletion of DDVP under 254â¯nm UV irradiation was ascribed to direct photodegradation and oxygen mediated photoinduced reactions. Direct photodegradation of DDVP decreased with 254â¯nm irradiation reduction, highlighting the importance of radical mediated mechanisms at low irradiation doses. Based on LC/MS data, the main photoproducts under simulated solar light and UV-C irradiation were identified and potential reaction pathways were postulated. The three main identified products were o-methyl 2,2-dichlorovinyl phosphate, dichloroacetaldehyde and dimethylphosphate. Moreover, the toxicity of samples was evaluated along the irradiation exposure time using Microtox® assays. This study brings new insights into the role of oxygen in the photodegradation of DDVP and the induced and inhibition mechanisms involved in the presence of the humic acids in natural waters.