This study aimed at investigating the degradation of fungicide carbendazim (CBZ) via photo-Fenton reactions in artificially and solar irradiated photoreactors at laboratory scale and in a semi-pilot scale Raceway Pond Reactor (RPR), respectively. Acute toxicity was monitored by assessing the sensibility of bioluminescent bacteria (Aliivibrio fischeri) to samples taken during reactions. In addition, by-products formed during solar photo-Fenton were identified by liquid chromatography coupled to mass spectrometry (UFLC-MS). For tests performed in lab-scale, two artificial irradiation sources were compared (UV and UV-Vis). A complete design of experiments was performed in the semi-pilot scale RPR in order to optimize reaction conditions (Fe and HO concentrations, and water depth). Efficient degradation of carbendazim (> 96%) and toxicity removal were achieved via artificially irradiated photo-Fenton under both irradiation sources. Control experiments (UV photolysis and UV-Vis peroxidation) were also efficient but led to increased acute toxicity. In addition, HO/UV required longer reaction time (60 minutes) when compared to the photo-Fenton process (less than 1 min). While Fenton's reagent achieved high CBZ and acute toxicity removal, its efficiency demands higher concentration of reagents in comparison to irradiated processes. Solar photo-Fenton removed carbendazim within 15 min of reaction (96%, 0.75 kJ L), and monocarbomethoxyguanidine, benzimidazole isocyanate, and 2-aminobenzimidazole were identified as transformation products. Results suggest that both solar photo-Fenton and artificially irradiated systems are promising routes for carbendazim degradation.
This work investigated an innovative alternative to improve municipal wastewater treatment plant effluent (MWWTP effluent) quality aiming at the removal of contaminants of emerging concern (caffeine, carbendazim, and losartan potassium), and antibiotic-resistant bacteria (ARB), as well as disinfection (E. coli). Persulfate was used as an alternative oxidant in the solar photo-Fenton process (solar/Fe/S2O82−) due to its greater stability in the presence of matrix components. The efficiency of solar/Fe/S2O82− at neutral pH using intermittent iron additions is unprecedented in the literature. At first, solar/Fe/S2O82− was performed in a solar simulator (30 W m−2) leading to more than 60% removal of CECs, and the intermittent iron addition strategy was proved effective. Then, solar/Fe/S2O82− and solar/Fe/H2O2 were compared in semi-pilot scale in a raceway pond reactor (RPR) and a cost analysis was performed. Solar/Fe/S2O82− showed higher efficiencies of removal of target CECs (55%), E. coli (3 log units), and ARB (3 to 4 log units) within 1.9 kJ L−1 of accumulated irradiation compared to solar/Fe/H2O2 (CECs, 49%; E. coli, 2 log units; ARB, 1 to 3 log units in 2.5 kJ L−1). None of the treatments generated acute toxicity upon Allivibrio fischeri. Lower total cost was obtained using S2O82− (0.6 € m−3) compared to H2O2 (1.2 € m−3). Therefore, the iron intermittent addition aligned to the use of persulfate is suitable for MWWTP effluent quality improvement at neutral pH.
This study sought to evaluate and propose adjustments to the water quality monitoring network of surface freshwaters in the Paraopeba river basin (Minas Gerais, Brazil), using multivariate statistical methods. A total of 13,560 valid data were analyzed for 19 water quality parameters at 30 monitoring sites, over a period of 5 years (2008-2013). The cluster analysis grouped the monitoring sites in eight groups based on similarities of water quality characteristics. This analysis made it possible to detect the most relevant monitoring stations in the river basin. The principal components analysis associated with non-parametric tests and the analysis of violation of the standards prescribed by law, allowed for identifying the most relevant parameters which must be maintained in the network (thermotolerant coliforms, total manganese, and total phosphorus). The discharge of domestic sewage and industrial wastewater, that from mining activities and diffuse pollution from agriculture and pasture areas are the main sources of pollution responsible for the surface water quality deterioration in this basin. The BP073 monitoring site presents the most degraded water quality in the Paropeba river basin. The monitoring sites BP094 and BP092 are located geographically close and they measure similar water quality, so a possible assessment of the need to maintain only one of the two in the monitoring network is suggested. Therefore, multivariate analyses were efficient to assess the adequacy of the water quality monitoring network of the Paraopeba river basin, and it can be used in other watersheds.
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