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A modified quick, easy, cheap, effective, rugged, and safe (QuEChERS) method was established for simultaneous quantification of eight pharmaceutical molecules (2-hydroxyibuprofen, diclofenac, ibuprofen, propranolol, ofloxacin, oxazepam, sulfamethoxazole, carbamazepine) and caffeine in environmental matrices. Analysis was performed by ultra-high-performance liquid chromatography with tandem mass spectrometry (UHPLC-MS-MS). Quantification was performed by using the 13C internal standard method for each molecule. Two methods were firstly optimized on freeze-dried waste activated sludge and then applied and validated on real complex matrices, which have contrasted physicochemical properties, i.e., clarified wastewater and primary sludge. The combination of acetate buffer with MgSO4 (protocol A) and citrate buffer with Na2SO4 (protocol B) was found necessary to recover the nine targeted compounds. Adding a higher salts quantity of Na2SO4 (protocol B) compared to MgSO4 (protocol A) is crucial to increase the ionic strength of the aqueous solution and to obtain comparable extraction recoveries of the targeted molecules. Adding two times solvent volume to the aqueous phase leads to increased absolute recovery for all molecules and both protocols. After demonstration of the final protocol's performance on the control matrix, its robustness was tested on the matrices of interest. As a result, the two proposed detection methods exhibit good reproducibility, high sensitivity, and high reliability.
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The removal of polycyclic aromatic hydrocarbons (PAHs) in activated sludge was evaluated using two laboratory-scale bioreactors, coupled or not with a disintegration system (sonication). Mass balances performed on each system underlined that PAHs removal was significantly improved after sludge disintegration, especially for the higher molecular weight PAHs studied, which tended to adsorb to suspended matter. A model was developed in order to study the effect of sludge disintegration on the content of dissolved and colloidal matter (DCM), and to predict the potential impacts on PAHs availability and degradation. Results showed that this new model was efficient for capturing apparent degradation improvement trends and for discriminating between the involved mechanisms. This study showed that DCM content increased after sludge disintegration, and proved to be the main driver for improving PAHs apparent degradation.
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Hidrocarburos Policíclicos Aromáticos , Aguas del Alcantarillado , Reactores BiológicosRESUMEN
In industry, treatments against biofilms need to be optimized and, in the wastewater treatment field, biofilm composition needs to be controlled. Therefore, describing the biochemical and physical structures of biofilms is now required to better understand the influence of operating parameters and treatment on biofilms. The present study aims to investigate how growth conditions influence EPS composition, biofilm physical properties and volume detachment using a 1D biofilm model. Two types of EPS are considered in the present model, proteins and polysaccharides. The main hypotheses are that: (i) the production of polysaccharides occurs mainly under strong nutrient limitation(s) while the production of proteins is coupled to both the substrate uptake rate and the lysis process; (ii) the local biofilm porosity depends on the local biofilm composition. Both volume and surface detachment occur in biofilms and volume detachment extent depends on the biofilm local cohesion and thus on the local composition of biofilms for a given shear stress. The model is based on experimental trends and aims to represent these observations on the basis of biochemical and physical processes. Four case studies covering a wide range of contrasting growth conditions such as different COD/N ratios, applied SOLR and shear stresses are investigated. The model predicts how the biochemical and physical biofilm structures change as a result of contrasting growth conditions. More precisely simulation results are in good agreement with the main experimental observations reported in the literature, such as: (i) a strong nitrogen limitation of growth induces an important accumulation of polysaccharides leading to a more porous and homogenous biofilm, (ii) a high applied surface organic loading load allows to obtain a high biofilm thickness, (iii) a strong shear stress applied during the biofilm growth leads to a reduction of the biofilm thickness and to a consolidation of the biofilm structure. Overall, this model represents a relevant decision tool for the selection of appropriate enzymatic treatments in the context of negative biofilm control. From our results, it appears that protease based treatments should be more appropriate for biofilms developed under low COD/N ratios (about 20 gCOD/gN) whereas both glucosidases and proteases based treatments should be more appropriate for biofilms developed under high COD/N ratio (about 70 gCOD/gN). In addition, the model could be useful for other applications such as resource recovery in biofilms or granules, and help to better understand biological membrane fouling.
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Biopelículas , Polisacáridos , Proteínas , Simulación por Computador , Estrés MecánicoRESUMEN
The removal efficiency of nine pharmaceutical compounds from primary sludge was evaluated in two different operating conditions: (i) in conventional Mesophilic Anaerobic Digestion (MAD) alone and (ii) in a co-treatment process combining Mesophilic Anaerobic Digestion and a Thermophilic Aerobic Reactor (MAD-TAR). The pilot scale reactors were fed with primary sludge obtained after decantation of urban wastewater. Concerning the biodegradation of organic matter, thermophilic aeration increased solubilization and hydrolysis yields of digestion, resulting in a further 26% supplementary removal of chemical oxygen demand (COD) in MAD-TAR process compared to the conventional mesophilic anaerobic digestion. The highest removal rate of target micropollutants were observed for caffeine (CAF) and sulfamethoxazole (SMX) (>89%) with no substantial differences between both processes. Furthermore, MAD-TAR process showed a significant increase of removal efficiency for oxazepam (OXA) (73%), propranolol (PRO) (61%) and ofloxacine (OFL) (41%) and a slight increase for diclofenac (DIC) (4%) and 2 hydroxy-ibuprofen (2OH-IBP) (5%). However, ibuprofen (IBP) and carbamazepine (CBZ) were not degraded during both processes. Anaerobic digestion affected the liquid-solid partition of most target compounds. Sorbed fraction of pharmaceutical compounds on the sludge tend to decrease after digestion, this tendency being more pronounced in the case of the MAD-TAR process due to much lower concentration of solids.
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Preparaciones Farmacéuticas , Eliminación de Residuos Líquidos , Anaerobiosis , Análisis de la Demanda Biológica de Oxígeno , Reactores Biológicos , Aguas del Alcantarillado/análisis , TemperaturaRESUMEN
The partitioning between solids and the aqueous phase largely controls the fate of PAH compounds in biological treatment. The prediction of PAH sorption behaviour into activated sludge was investigated here. The suitability of a three-compartment model to describe partitioning in such a complex matrix was first evaluated by adding increasing quantities of dissolved and colloidal matter (DCM) (from 0 to 34.9% of the total matter). In a range of DCM concentrations varying from 0 to 1.4â¯gâ¯L-1, the PAH aqueous fraction, including both freely dissolved and sorbed to DCM molecules, increased from 9.9% to 33% for naphthalene (the most soluble PAH) and from 0.29% to 13.3% for indeno(1,2,3,c,d)pyrene (the least soluble PAH tested). The sorption of PAHs on dissolved and colloidal matter (DCM) was assessed by determining two partitioning constants (KPART and KDCM) for the 16 PAHs listed by the US EPA. New experiments were carried out for model validation and show that the model properly predicts the PAH partitioning following sludge disintegration by sonication.
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Hidrocarburos Policíclicos Aromáticos/metabolismo , Aguas del Alcantarillado/química , Contaminantes Químicos del Agua/química , Hidrocarburos Policíclicos Aromáticos/análisis , Contaminantes Químicos del Agua/análisisRESUMEN
This study compared two anammox sequencing batch reactors (SBR) for one year. SBRconstantT was kept at 30⯰C while temperature in SBRloweringT was decreased step-wise from 30⯰C to 20⯰C and 15⯰C followed by over 140â¯days at 12.5⯰C and 10⯰C. High retention of anammox bacteria (AnAOB) and minimization of competition with AnAOB were key. 5-L anoxic reactors with the same inoculum were fed synthetic influent containing 25.9â¯mg NH4+-N/L and 34.1â¯mg NO2--N/L (no COD). Specific ammonium removal rates continuously increased in SBRconstantT, reaching 785â¯mg NH4+-N/gVSS/d, and were maintained in SBRloweringT, reaching 82.2 and 91.8â¯mg NH4+-N/gVSS/d at 12.5 and 10⯰C respectively. AnAOB enrichment (increasing hzsA and 16S rDNA gene concentrations) and adaptation (shift from Ca. Brocadia to Ca. Kuenenia in SBRloweringT) contributed to these high rates. Rapidly settling granules developed, with average diameters of 1.2 (SBRconstantT) and 1.6â¯mm (SBRloweringT). Results reinforce the potential of anammox for mainstream applications.
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Reactores Biológicos , Compuestos de Amonio , Nitrógeno , Oxidación-Reducción , TemperaturaRESUMEN
The aerobic biological process is one of the best technologies available for removing hazardous organic substances from industrial wastewaters. But in the case of volatile organic compounds (benzene, toluene, ethylbenzene, p-xylene, naphthalene), volatilization can contribute significantly to their removal from the liquid phase. One major issue is to predict the competition between volatilization and biodegradation in biological process depending on the target molecule. The aim of this study was to develop an integrated dynamic model to evaluate the influence of operating conditions, kinetic parameters and physical properties of the molecule on the main pathways (biodegradation and volatilization) for the removal of Volatile Organic Compounds (VOC). After a comparison with experimental data, sensitivity studies were carried out in order to optimize the aerated biological process. Acclimatized biomass growth is limited by volatilization, which reduces the bioavailability of the substrate. Moreover, the amount of biodegraded substrate is directly proportional to the amount of active biomass stabilized in the process. Model outputs predict that biodegradation is enhanced at high SRT for molecules with low H and with a high growth rate population. Air flow rate should be optimized to meet the oxygen demand and to minimize VOC stripping. Finally, the feeding strategy was found to be the most influential operating parameter that should be adjusted in order to enhance VOC biodegradation and to limit their volatilization in sequencing batch reactors (SBR).