RESUMEN
Cork boiling wastewater is a very complex mixture of naturally occurring compounds leached and partially oxidized during the boiling cycles. The effluent generated is recalcitrant and could cause a significant environmental impact. Moreover, if this untreated industrial wastewater enters a municipal wastewater treatment plant it could hamper or reduce the efficiency of most activated sludge degradation processes. Despite the efforts to treat the cork boiling wastewater for reusing purposes, is still not well-known how safe these compounds (original compounds and oxidation by-products) will be. The purpose of this work was to apply an HPLC-high resolution mass spectrometry method and subsequent non-target screening using a multivariate analysis method (PCA), to explore relationships between samples (treatments) and spectral features (masses or compounds) that could indicate changes in formation, degradation or polarity, during coagulation/flocculation (C/F) and photo-Fenton (PhF). Although, most of the signal intensities were reduced after the treatment line, 16 and 4 new peaks were detected to be formed after C/F and PhF processes respectively. The use of this non-target approach showed to be an effective strategy to explore, classify and detect transformation products during the treatment of an unknown complex mixture.
RESUMEN
Industrial preparation of cork consists of its immersion for approximately 1 hour in boiling water. The use of herbicides and pesticides in oak tree forests leads to absorption of these compounds by cork; thus, after boiling process, they are present in wastewater. Cork boiling wastewater shows low biodegradability and high acute toxicity involving partial inhibition of their biodegradation when conventional biological treatment is applied. In this work, a treatment line strategy based on the combination of advanced physicochemical technologies is proposed. The final objective is the reuse of wastewater in the cork boiling process; thus, reducing consumption of fresh water in the industrial process itself. Coagulation pre-treatment with 0.5 g/L of FeCl3 attained the highest turbidity elimination (86 %) and 29 % of DOC elimination. Similar DOC removal was attained when using 1 g/L of ECOTAN BIO (selected for ozonation tests), accompanied of 64 % of turbidity removal. Ozonation treatments showed less efficiency in the complete oxidation of cork boiling wastewater, compared to solar photo-Fenton process, under the studied conditions. Nanofiltration system was successfully employed as a final purification step with the aim of obtaining a high-quality reusable permeate stream. Monitoring of unknown compounds by LC-QTOF-MS allowed the qualitative evaluation of the whole process. Acute and chronic toxicity as well as biodegradability assays were performed throughout the whole proposed treatment line.
Asunto(s)
Residuos Industriales , Reciclaje/métodos , Aguas Residuales/química , Contaminantes Químicos del Agua/química , Purificación del Agua/métodos , Cloruros/química , Compuestos Férricos/química , Peróxido de Hidrógeno/química , Oxidación-Reducción , Ozono/química , Contaminantes Químicos del Agua/toxicidadRESUMEN
Solar photo-Fenton process has been extensively reported to be highly efficient in the remediation of complex industrial wastewater containing several families of pollutants such as pharmaceuticals, dyes, pesticides, derivatives of wine, etc. Moreover, solar photo-Fenton mathematical modelling regarded as a powerful tool for scaling-up and process control purposes is hindered by the complexity and variability of its reaction mechanism which depends on the particular wastewater under study. In this work, non-biodegradable cork boiling wastewater has been selected as a case study for solar photo-Fenton dynamic modelling by using MATLAB® software. First of all physic-chemical pretreatment was applied attaining chemical oxygen demand (COD) reductions between 43 and 70 % and total suspended solid (TSS) reductions between 23 % and 59 %. After solar photo-Fenton treatment, COD decreased between 45 and 90 % after consumptions of H2O2 varying around 1.9 and 2.4 g/L. Individual calibration of the semi-empirical model by using experimental results made it possible to perfectly predict hydrogen peroxide variations throughout the treatment. It must be highlighted that slight deviations between predictions and experimental data must be attributed to important changes in wastewater characteristics.
Asunto(s)
Eliminación de Residuos Líquidos/métodos , Aguas Residuales/química , Contaminantes Químicos del Agua/química , Análisis de la Demanda Biológica de Oxígeno , Peróxido de Hidrógeno , Residuos Industriales/análisis , Proyectos Piloto , Luz SolarRESUMEN
The thermal Diels-Alder cycloadditon reaction of diethyl 2-[cyano(toluene-4-sulfinyl)methylene]propanedioate, C(16)H(17)NO(5)S, with cyclopentadiene gave the pure racemates of two of the four possible diastereomers, with a complete pi-facial selectivity and a high (80:20) endo/exo-sulfinyl selectivity. X-ray diffraction studies of diethyl 2-[cyano(toluene-4-sulfinyl)methylene]propanedioate and the major isomer of the cycloaddition product, namely diethyl 3-cyano-3-(toluene-4-sulfinyl)bicyclo[2.2.1]hepta-5-ene-2,2-dicarboxylate, C(21)H(23)NO(5)S, reveal that the conformation of the substituents on the acrylonitrile moiety produces both steric and electronic effects, which affect the stereoselectivity of the reaction.
RESUMEN
A new kind of chiral dienophiles, cyclic vinyl-p-tolylsulfilimines (2a and 2b), were obtained from the corresponding (Z)-sulfinylacrylonitriles with HBF(4) and methanol. The asymmetric Diels-Alder reaction of optically pure 2a with cyclopentadiene under mild thermal or catalyzed conditions afforded only the endo-4a adduct with complete endo and pi-facial selectivities. The ability of the sulfilimine moiety to enhance the dienophilic reactivity of the double bond is similar to that of the sulfinyl group.
RESUMEN
The (-)-S isomer of 5-benzoyl-1,2-dihydro-3H-pyrrolo[1,2-alpha]pyrrole-1-carboxylic acid is about 60 times more potent than the (+)-R isomer in the carrageenan edema test and ca. 230 times more active than the (+)-R isomer in the mouse phenylquinone writhing assay.