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The adsorption process efficiently removes per- and polyfluoroalkyl substances (PFAS) from water, but managing exhausted adsorbents presents notable environmental and economic challenges. Conventional disposal methods, such as incineration, may reintroduce PFAS into the environment. Therefore, advanced regeneration techniques are imperative to prevent leaching during disposal and enhance sustainability and cost-effectiveness. This review critically evaluates thermal and chemical regeneration approaches for PFAS-laden adsorbents, elucidating their operational mechanisms, the influence of water quality parameters, and their inherent advantages and limitations. Thermal regeneration achieves notable desorption efficiencies, reaching up to 99% for activated carbon. However, it requires significant energy input and risks compromising the adsorbent's structural integrity, resulting in considerable mass loss (10-20%). In contrast, chemical regeneration presents a diverse efficiency landscape across different regenerants, including water, acidic/basic, salt, solvent, and multi-component solutions. Multi-component solutions demonstrate superior efficiency (>90%) compared to solvent-based solutions (12.50%), which, in turn, outperform salt (2.34%), acidic/basic (1.17%), and water (0.40%) regenerants. This hierarchical effectiveness underscores the nuanced nature of chemical regeneration, significantly influenced by factors such as regenerant composition, the molecular structure of PFAS, and the presence of organic co-contaminants. Exploring the conditional efficacy of thermal and chemical regeneration methods underscores the imperative of strategic selection based on specific types of PFAS and material properties. By emphasizing the limitations and potential of particular regeneration schemes and advocating for future research directions, such as exploring persulfate activation treatments, this review aims to catalyze the development of more effective regeneration processes. The ultimate goal is to ensure water quality and public health protection through environmentally sound solutions for PFAS remediation efforts.
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Notable differences in photo-physical and chemical properties were found between bulk water and solid phase extraction (SPE) isolates for dissolved organic matter (DOM). The moieties extracted using modified styrene divinylbenzene cartridges, which predominantly consist of conjugated aromatic molecules like humic acids, contribute mainly to light absorption but exhibit lower quantum yields of fluorescence and photo-produced reactive intermediates (PPRIs). Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) revealed lignin as the moieties displaying most significant variance in abundance. In Van Krevelen-Spearman plot, we observed molecules positively or negatively correlated with DOM's optical and photochemical properties (including SUVA254, steady-state concentrations of ·OH, 1O2 quantum yield, etc.) were confined to specific regions, which can be delineated using a threshold modified aromaticity index (AImod) of 0.3. Based on the relationships between optical properties and PPRI production, it is suggested that the energy gap between ground state and excited singlet state (â³ES1âS0), governing the inner conversion rate, serves as a determinant for apparent quantum yield of PPRIs in DOM, with intra-molecular charge transfer (CT) interactions potentially playing a pivotal role. Regarding DOM's photoreactivity with pollutants, this study has revealed, for the first time, that protein/amino sugars/amino acids could act as antioxidant groups in addition to phenols on the photolysis of sulfadiazine. These findings provide valuable insights into DOM photochemistry and are expected to stimulate further research in this area.
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Extração em Fase Sólida , Substâncias Húmicas , Compostos Orgânicos/químicaRESUMO
Covalent organic frameworks (COFs) demonstrate remarkable potential for adsorbing per/polyfluoroalkyl substances (PFAS). Nevertheless, the challenge of recycling powdered COFs hampers their practical application in water treatment. In this research, a quaternary amine COF with inherent positive surface charge was synthesised to adsorb perfluorooctanoic acid (PFOA) via electrostatic interactions. The COF was then combined with chitosan (CS) through a simple dissolution-evaporation process, resulting in a composite gel material termed COF@CS. The findings indicated that the adsorption capacity of COF@CS significantly surpassed that of the original COF and CS. According to the Langmuir model, COF@CS achieved a maximum PFOA capacity of 2.8 mmol g-1 at pH 5. Furthermore, the adsorption rate increased significantly to 6.2 mmol g-1 h-1, compared to 5.9 mmol g-1 h-1 for COF and 3.4 mmol g-1 h-1 for CS. Notably, COF@CS exhibited excellent removal efficacy for ten other types of PFAS. Moreover, COF@CS could be successfully regenerated using a mixture of 70% ethanol and 1 wt% NaCl, and it exhibited stable reusability for up to five cycles. X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) characterisation, and theoretical calculations revealed that the quaternary amine functional group in COF served as the primary adsorption site in the composite gel material, while the protonated amino group on CS enhanced PFOA adsorption through electrostatic interaction. This study highlights the significant practical potential of COF@CS in the removal of PFAS from aqueous solution and environmental remediation.
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Caprilatos , Quitosana , Fluorocarbonos , Estruturas Metalorgânicas , Poluentes Químicos da Água , Purificação da Água , Quitosana/química , Adsorção , Poluentes Químicos da Água/química , Fluorocarbonos/química , Purificação da Água/métodos , Caprilatos/química , Estruturas Metalorgânicas/químicaRESUMO
Adsorption is highly effective and desirable for the removal of per- and polyfluoroalkyl substances (PFAS) from water, and suitable pore size of porous adsorbents is important for efficient removal of PFAS, but the relationship between adsorbent pore size and PFAS adsorption remains unclear. In this study, five regular covalent organic frameworks (COFs) with distinct pore sizes were successfully synthesized, and the correlation between the pore size of COFs and PFAS length for efficient PFAS adsorption was investigated. Both excessively small and large pore sizes of COFs are not conducive to the efficient adsorption of PFAS due to the diffusion hindrance and weak binding forces. The COFs with a pore size ranging from 2.5 to 4.0 times of the PFAS molecular size demonstrated the most suitable for PFAS adsorption. This study also investigated the potential impact of nanobubbles on PFAS adsorption on orderly porous COFs through aeration and degassing treatment of the adsorption system. The bubbles on hydrophobic COFs were verified to be responsible for PFAS adsorption, another important adsorption mechanism of PFAS on COFs. The long-chain PFAS have stronger enrichment at the gas-liquid interface than the short-chain PFAS, resulting in higher adsorption capacity for long-chain PFAS.
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To predict PPCPs' photolysis rate in natural aquatic environment, it is essential to grasp the reaction rates between DOM and PPCPs, yet there are few measured data and no prediction models for this important photochemical parameter. To address this, a reaction rate coefficient (αDOM) was defined to describe the apparent rate of DOM-involved photoreaction for PPCPs. The measured αDOM values for 40 PPCPs in 9 DOM samples varied dramatically, ranging from (-2.1 ± 0.1)× 1010 to (2.2 ± 0.1)× 1011 M-1 s-1. Then the quantitative structure-activity relationship (QSAR) models were developed using chemical and water quality descriptors via the random forest method. We initially separated positive and negative values by a classifier with an AUC value of 0.965, followed by the construction of regression models for positive and negative values, respectively, using a regressor. Positive models achieved satisfactory goodness-of-fit and predictive ability (R2adj=0.92 and Q2ext=0.86), while negative models demonstrated acceptable performance (R2adj=0.71 and Q2ext=0.70). Finally, a comprehensive photolysis model that incorporates the QSAR models for αDOM was established and the significance of water quality parameters was emphasized through sensitive analysis. This model enables more elaborate predictions of PPCPs' photolysis rates in various water samples, providing valuable assistance for forecasting PPCPs' environmental fate.
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The attenuation characteristics of PPCPs play an important part in predicting their environmental concentrations. However, considerable uncertainty remains in reported laboratory data on the attenuation characteristics of PPCPs. In this analysis, we compile information on laboratory-observed photodegradation half-lives (t1/2), biodegradation t1/2, the organic carbon normalized adsorption constant (KOC) and field-observed overall attenuation t1/2 for PPCPs in water bodies from more than 200 peer-reviewed studies. To mitigate the effects of such uncertainty, we derive representative values (RV) for PPCP degradability from these records to better compare the characteristics of different PPCPs. We further examine the influence of experimental conditions and environmental drivers on the determination of t1/2 using difference analysis and correlation analysis. The results indicate that for laboratory photodegradation tests, different light sources, initial concentration and volume significantly affect t1/2, whereas there is no significant difference between values obtained from tests conducted in pure water and natural water. For biodegradation, laboratory-measured t1/2 values in batch, flume and column studies gradually decrease, marking the controlling role of experimental setup. Redox condition, initial concentration and volume are also recognized as important influencing factors. For adsorption, water-sediment ratio is the primary reaction parameter. As two frequently investigated factors, however, pH and temperature are not significant factors in almost all cases. In field observations, the persistence of carbamazepine, typically used as a tracer, is in doubt. Water depth and latitude are the most correlated drivers of t1/2, indicating the predominant status of photodegradation in the overall attenuation rates. These findings call for caution when selecting experimental parameters and environmental drivers in determining PPCP's attenuation rates and establishing PPCP fate models in the field.
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To determine and predict the reaction rate between 3DOM* and PPCPs in various water bodies, this study defines a reaction rate coefficient ( [Formula: see text] ) to describe the reaction between 3DOM* and PPCPs. As the values also included the inhibition effect of DOM's antioxidant moieties, the calculation of [Formula: see text] is inconsistent with that of a bimolecular rate constant via the steady-state kinetic method. The [Formula: see text] values of 12 selected PPCPs were determined in two DOM solutions and ten DOM-containing water samples collected from typical surface water bodies in Beijing. The Pearson coefficients between nine predictors including the absorbance ratio (E2/E3), specific absorption coefficient at 254 nm (SUVA254), fluorescence index (FI), biological index (BIX), humification index (HIX), pH, total organic carbon (TOC), total fluorescence intensity (TFI) and TOC normalized TFI (TFI/TOC) and [Formula: see text] were examined. Correlation patterns for sulfonamides, ß-blockers and diclofenac supported the electron transfer pathway, and was distinctly different from those appeared for FQs where quenching effect played a main part. TFI and TFI/TOC were recognized as the most useful surrogates in empirically predicting [Formula: see text] . For PPCPs that went through the electron transfer pathway, [Formula: see text] could be well fit to the Rehm-Weller model assuming a proportional relationship between TFI and â³Get. For FQs, [Formula: see text] was found to linearly correlated with TFI/TOC. The [Formula: see text] values determined in this study enrich the database of PPCPs photolysis parameters, and the correlation analysis provides reference for forecasting PPCPs fate in the aquatic environment.
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Highly efficient oxidation, as non-thermal regeneration technology, is a promising method to solve the regeneration problem of spent activated carbon (AC) in wastewater treatment. In this study, FeOCl was confined into activated carbon (FeOCl/AC) for catalytic oxidation of contaminants on AC during the regeneration process. The characterization results of FeOCl/AC showed that amorphous FeOCl was distributed in micropores, mesopores and macropores of AC. The methylene blue (MB)-adsorbed FeOCl/AC had a regeneration efficiency of 93.7 % at neutral pH in the presence of H2O2, much higher than 46.9 % by Fenton oxidation and 33.7 % by H2O2 oxidation. Meanwhile, the spent FeOCl/AC after the adsorption of atrazine, 2,4-dichlorophenol, and ofloxacin had the regeneration efficiencies of 71.5 %, 86.4 %, and 100 %, respectively. Moreover, the regeneration efficiency still reached 87 % in the fifth adsorption-regeneration cycle, and was linearly decreased with the increase of adsorbed amounts of MB. During 6 h regeneration of spent FeOCl/AC, 97 % of adsorbed MB was degraded. Electron paramagnetic resonance and radical trapping experiments indicated that both superoxide and hydroxyl radicals were involved in MB oxidation during the regeneration process.
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Atrazina , Poluentes Químicos da Água , Carvão Vegetal/química , Peróxido de Hidrogênio/química , Azul de Metileno/química , Superóxidos , Oxirredução , Adsorção , OfloxacinoRESUMO
This paper aims to provide insights on mechanochemistry as a green and versatile tool to synthesize advanced materials for water remediation. In particular, mechanochemical methodologies for preparation of reagents and catalysts for the removal of organic pollutants are reviewed and discussed, focusing on those materials that, directly or indirectly, induce redox reactions in the contaminants (i.e., photo-, persulfate-, ozone-, and Fenton-catalysts, as well as redox reagents). Methods reported in the literature include surface reactivity enhancement for single-component materials, as well as multi-component material design to obtain synergistic effects in catalytic efficiency and/or reactivity. It was also amply demonstrated that mechanochemical surface activation or the incorporation of catalytic/reactive components boost the generation of reactive species in water by accelerating charge transfer, increasing superficial active sites, and developing pollutant absorption. Finally, indications for potential future developments in this field are debated.
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Poluentes Ambientais , Água , Catálise , Descontaminação , Indicadores e Reagentes , OxirreduçãoRESUMO
Adsorption is an effective method for the removal of perfluoroalkanesulfonates (PFSAs) from water, and the limitation of the adsorption rate of existing adsorbents motivates efforts to develop novel adsorbents. Here, we developed four ß-cyclodextrin covalent organic frameworks (ß-CD-COFs) with a rapid removal rate and high adsorption capacity for four PFSAs in water including perfluorooctanesulfonate (PFOS), perfluorobutanesulfonate (PFBS), perfluorohexanesulfonate (PFHxS), and chlorinated polyfluorinated ether sulfonate (F53B). All ß-CD-COFs exhibited extremely fast adsorption (adsorption equilibrium <2 min) for PFSAs with high adsorption capacities (0.33-1.51 mmol/g), which were significantly better than those of traditional resins and activated carbons, probably due to the ordered pores of ß-CD-COFs and the electron-deficient cavity ß-CD. Density functional theory (DFT) calculations also showed that PFSAs could be captured in the ß-CD cavity through strong interactions with a high binding energy. The novel ß-CD-COFs were highly selective to PFSAs in simulated wastewater impacted by aqueous film-forming foams, and they could also rapidly remove them from an actual chrome plating wastewater within 2 min. Additionally, the ß-CD-COFs could be regenerated by methanol with relatively good reusability in four cycles, further highlighting their application potential as PFAS adsorbents in water or wastewater.
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Per- and polyfluoroalkyl substances (PFAS) are ubiquitous in aquatic environments around the world. In recent years, the enrichment of PFAS on the surface of nanobubbles on adsorbents has been proposed, but no direct evidence has been provided to support this new adsorption mechanism. In this study, we used density functional theory (DFT) and molecular dynamics (MD) to simulatively investigate the contribution of nanobubbles for PFAS adsorption on the pristine and functionalized graphene (GR). The adsorption energy of PFAS on GR-NH2 was higher than that of GR-OH, while GR showed the lowest adsorption energy. When the effect of water molecules was considered, the oleophobic property of the C-F chain made it difficult for hydrophobic interaction to be involved in the adsorption of PFAS on nonpolar GR. With the existence of nanobubbles, both GR and GR-NH2 can effectively remove PFAS, but their adsorption mechanisms were quite different. For hydrophobic GR, the nanobubbles initially attached to the surface of materials played a major role, while for hydrophilic GR-NH2, the nanobubbles dispersed in the solution were more important. Moreover, the nanobubbles had a more significant contribution to long-chain PFAS. Our degassing and aeration experiments could support the simulation results. The removal of PFOS decreased by 27.7% at maximum after degassing and increased by 21.0%-29.2% after aeration. The study could provide a theoretical basis for the environmental process and contamination control of PFAS at the solid-liquid interfaces.
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Fluorocarbonos , Grafite , Poluentes Químicos da Água , Adsorção , Fluorocarbonos/análise , Hidróxidos , Poluentes Químicos da Água/análiseRESUMO
The capacitive deionization (CDI) technology was adopted to reduce the low concentrations of nickel in electroplating wastewater to meet the discharge standard. The composite anode and the composite cathode (Resin-CGA) were prepared by incorporating anion-exchange resin (AR-CGA) and cation exchange resin (CR-CGA) into the titanium mesh by the conductive graphite adhesive, respectively. The electrolytic performances of the Resin-CGA electrodes at different cell voltages, initial electrolyte pH and initial nickel concentrations were investigated. The adsorbed amount of nickel on the CR-CGA electrodes and the removal percentage of nickel were 0.095 mg g-1 and 95%, respectively. The Ni2+ concentrations were reduced to 0.005 mg L-1 and the electricity consumption was 1.6 kWh per ton of the electroplating wastewater at the initial Ni2+ concentrations of 1.0 mg L-1 under the optimal conditions, exhibiting better electrolytic performance than the cation-exchange resin and the electrodes prepared by the conductivity graphite adhesive (CGA). In addition, the spent electrodes were electrochemically regenerated and the electrolytic performance of the Resin-CGA electrodes kept stable during the cycles. This study provided a promising method to reduce the low concentrations of Ni2+ to less than 0.1 mg L-1 in the treatment of electroplating wastewater.
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Águas Residuárias , Purificação da Água , Eletrodos , Galvanoplastia , Íons , Níquel/análise , Tecnologia , Águas Residuárias/análiseRESUMO
Trichloropropyl phosphate (TCPP) as a widely used typical chlorinated organophosphate flame retardant has received significant attention because of its widespread presence in water and negative effects on human health. In this study, a ball-milling method was used to prepare a magnetic powdered carbon adsorbent (PC/nano-Fe3O4 composite) for TCPP removal via adsorption and catalytic degradation. The effect of Fe3O4 content on TCPP adsorption and degradation performance by PC/nano-Fe3O4 composite was investigated. The PC/nano-Fe3O4 composite prepared by high Fe3O4 content (25%) was not favorable for TCPP adsorption and degradation. However, the PC/Fe3O4 containing low Fe3O4 content (10%) had insufficient magnetic separation ability from water. The synthesized PC/nano-Fe3O4 composite with a Fe3O4/PC mass ratio of 1/5 exhibited a maximum adsorption capacity of 2682.1 µg/g as well as a complete TCPP degradation within 3 h in a Fenton-like system. Moreover, the possible break sites of TCPP and its degradation pathway were proposed based on theoretical calculation and experimental analysis. Regeneration studies showed that PC/nano-Fe3O4 composite had high reusability and adsorption capacity in six cycles, while its catalytic performance declined in the multiple reuse cycles. This strategy could be extended to prepare other magnetic powdered adsorbents for organic pollutant adsorption and degradation.
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Poluentes Químicos da Água , Água , Adsorção , Carbono , Humanos , Fenômenos Magnéticos , Organofosfatos , Fosfatos , Pós , Poluentes Químicos da Água/análiseRESUMO
Photocatalytic degradation of typical pharmaceuticals in natural sunlight and in actual water is of great significance. In this study, the oxygen or nitrogen linked heptazine-base polymer (ONLH) was successfully incorporated with TiO2 nanoparticles and formed a TiO2/ONLH nanocomposite which was responded to the natural sunlight. Under natural sunlight, the TiO2/ONLH can effectively degrade ten types of pharmaceuticals. In particular, fluoroquinolone containing N-piperazinyl, and cardiovascular drugs containing long aromatic side chains were easily degraded. The half-life of the best degradation performance of propranolol was less than 5 min. The rate constants of propranolol using the TiO2/ONLH were approximately six- and eight-fold higher than those of pristine TiO2 and ONLH, respectively. Two reactive species (OH and O2-) facilitated the rapid degradation of propranolol, which occurred primarily through the hydroxyl radical addition, ring-opening, and ipso substitution reactions. An acute toxicity test using luminescent bacteria indicated that the toxicity of the propranolol reaction solution gradually decreased with lower total organic carbon (TOC). According to the toxicity evaluation of monomer products, the TiO2/ONLH also reduced the generation of toxic transformation products. The effects of actual water/wastewater have further shown the TiO2/ONLH might be applied for the removal of pharmaceuticals in wastewater.
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Preparações Farmacêuticas , Poluentes Químicos da Água , Catálise , Luz Solar , Titânio , Água , Poluentes Químicos da Água/análiseRESUMO
The low concentration of nickel in electroplating wastewater is difficult to treat to meet the discharge standard. In this study, a commercial cation exchange membrane was used to combine the electrodialysis on a titanium plate anode sintered ruthenium-iridium and the electrodeposition on a stainless steel cathode to reduce the nickel concentration to less 0.1 mg L-1. The electrolytic properties of the electrodialysis combined with the electrodeposition were investigated at different cell voltages, electrolysis time, initial electrolyte pH, electrolyte flow rates and initial Ni2+ concentrations. The results indicated that the Ni2+ concentration in the anolyte and the catholyte could be reduced to 0.015 and 0.085 mg L-1, respectively, with the initial Ni2+ concentration of 1.0 mg L-1, which could meet the most strict Ni2+ discharge standard of 0.1 mg L-1. The electrodeposition of Ni2+ on the cathode enhanced the migration of the Ni2+ in the electrolytes, which was beneficial to decrease the energy consumption. Therefore, the combination of electrodialysis and electrodeposition was promising to reduce the low concentration of Ni2+ in the electroplating wastewater.
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Galvanoplastia , Águas Residuárias , Eletrólise , Íons , Níquel/análise , Águas Residuárias/análiseRESUMO
The ultraviolet/chlorine (UV/Cl2) process is an emerging advanced oxidation technology for micropollutant abatement in water and wastewater treatment. However, the application of the conventional UV/Cl2 process in decentralized systems is limited by the transport and management of liquid chlorine. To overcome this limitation, this study evaluated an electrochemically driven UV/Cl2 (E-UV/Cl2) process for micropollutant abatement under conditions simulating decentralized water treatment. The E-UV/Cl2 process combines UV irradiation with in situ electrochemical Cl2 production from anodic oxidation of chloride (Cl-) in source waters. The results show that with typical Cl- concentrations present in water sources for decentralized systems (30-300 mg/L Cl-), sufficient amounts of chlorine could be quickly electrochemically produced at the anode to enable E-UV/Cl2 process for water treatment. Due to its multiple mechanisms for micropollutant abatement (direct photolysis, direct electrolysis, Cl2-mediated oxidation, as well as hydroxyl radical and reactive chlorine species oxidation), the E-UV/Cl2 process effectively eliminated all micropollutants (trimethoprim, ciprofloxacin, metoprolol, and carbamazepine) spiked in a surface water in 5 min. In contrast, at least one micropollutant with â¼20-80% residual concentrations could still be detected in the water treated by 10 min of UV irradiation, chlorination, electrolysis, and the conventional UV/Cl2 process under similar experimental conditions. The electrical energy per order (EEO) for micropollutant abatement ranged from 0.15 to 1.8 kWh/m3 for the E-UV/Cl2 process, which is generally comparable to that for the conventional UV/Cl2 process (0.14-2.7 kWh/m3). These results suggest that by in-situ generating Cl2 from anodic oxidation of Cl-, the E-UV/Cl2 process can overcome the barrier of the conventional UV/Cl2 process and thus provide a promising technology for micropollutant abatement in decentralized water treatment systems.
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Poluentes Químicos da Água , Purificação da Água , Cloro , Oxirredução , Raios Ultravioleta , Águas Residuárias/análiseRESUMO
Pharmaceutically active compounds (PhACs) are widely found in the environment due to vast human consumption. Lots of work has been devoted to investigating the occurrence and seasonal variations globally. To fully understand characteristics and cross-year variation of PhACs in Beijing, 35 PhACs were analyzed in 46 sites across Beijing from both urban and suburban areas. Concentrations of target PhACs were ranged from levels of ng L-1 to µg L-1. Metoprolol (524 ng L-1), caffeine (390 ng L-1) and acetaminophen (156 ng L-1) were the three most abundant non-antibiotics with the highest median concentration, and nalidixic acid (135 ng L-1), erythromycin (64 ng L-1) and sulfamethoxazole (77 ng L-1) were the most abundant antibiotics. Urban and suburban areas are distinguished by PhAC composition in cluster analysis due to different wastewater collection rate. The ratio of easily removable compound group and hardly removable group was then proposed to reflect the wastewater collection rate. The compositional comparison of PhACs in WWTPs' effluents and their receiving rivers further illustrates the impact of WWTPs in urban area. Higher proportion of antibiotics (>30%) in suburban area reflected the impact of presence of livestock farms, which should be concerned. Further statistical analyses show an improving trend of wastewater collection rate, and excluding metoprolol, an anti-hypertension medicine, the total concentration of 13 target PhACs was reduced by 72% during 2013-2017.
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Preparações Farmacêuticas , Poluentes Químicos da Água/análise , Pequim , China , Monitoramento Ambiental , Humanos , Rios , Águas Residuárias , ÁguaRESUMO
A novel fibrous adsorbent (DAVSF-CA) was synthesized via grafting caffeic acid (CA) onto dialdehyde viscose staple fiber (DAVSF), and used to selectively adsorb Au(III) from simulated wastewater. Fourier Transform Infrared (FTIR), X-ray Photoelectron (XPS) and Nuclear Magnetic Resonance (NMR) spectra confirmed that caffeic acid was successfully grafted on DAVSF through condensation reaction. Adsorption experiments revealed that the adsorption of Au(III) on DAVSF-CA was extremely dependent on pH values and temperatures, and the maximum adsorption capacity of 3.71 mmol/g for Au(III) was obtained at pH 3.0 and 333 K according to the Langmuir fitting. High temperature was favorable for Au(III) adsorption because the adsorption of Au(III) on the DAVSF-CA was endothermic. The competitive adsorption demonstrated that DAVSF-CA had a good preference to Au(III) adsorption in the presence of some coexisting pollutants. The adsorption isotherm data of Au(III) were well-described by the Langmuir model, while the kinetic data were fitted well by the Pseudo-second-order equation. The major reaction involving the reduction of Au(III) to Au(0) was identified by XPS and XRD analysis. Namely, Au(III) was first captured on protonated functional groups via electrostatic adsorption, and then reduced to its elemental form and formed the nano-particles on the adsorbent surfaces.
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Adsorção , Ácidos Cafeicos/química , Celulose/química , Ouro/isolamento & purificação , Águas Residuárias/química , Poluentes Químicos da Água/isolamento & purificação , Concentração de Íons de Hidrogênio , Cinética , Oxirredução , Temperatura , Poluentes Químicos da Água/químicaRESUMO
Contamination of drinking water by per- and polyfluoroalkyl substances (PFASs) is a worldwide problem. In this study, we for the first time revealed the role of the air-water interface in enhancing the removal of long-chain perfluoroalkyl carboxylic (PFCAs; CnF2n+1COOH, n ≥ 7) and perfluoroalkane sulfonic (PFSAs; CnF2n+1SO3H, n ≥ 6) acids, collectively termed as perfluoroalkyl acids (PFAAs), through combined aeration and adsorption on two kinds of activated carbon (AC). Aeration was shown to enhance the removal of long-chain PFAAs through adsorption at the air-water interface and subsequent adsorption of PFAA-enriched air bubbles to the AC. The removal of selected long-chain PFAAs was increased by 50-115 % with the assistance of aeration, depending on the perfluoroalkyl chain length. Aeration is more effective in enhancing long-chain PFAA removal as air-water interface adsorption increases with PFAA chain length due to higher surface activity. After removing adsorbed air bubbles by centrifugation, up to 80 % of the long-chain PFAAs were able to desorb from the sorbent, confirming the contribution of the air-water interface to the adsorption of PFAAs on AC. Aeration during AC treatment of water could enhance the removal of long-chain PFAAs, and improve the performance of AC during water treatment.
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Ar/análise , Ácidos Carboxílicos/análise , Carvão Vegetal/química , Água Potável/química , Fluorocarbonos/análise , Ácidos Sulfônicos/análise , Poluentes Químicos da Água/análise , Purificação da Água/métodos , Adsorção , Modelos TeóricosRESUMO
The catalytic performance of Fe3O4/reduced graphene oxide (Fe3O4/rGO) nanocomposite makes it attractive for the removal of emerging pollutants from water, but the combination of its efficient adsorption and degradation of per- and polyfluoroalkyl substances has not been studied. Here we report the optimal granular Fe3O4/rGO with high thermal and acid resistance stability through controlling its self-assembly for the adsorption and degradation of sodium p-perfluorous nonenoxybenzene sulfonate (OBS) from water. The maximum adsorption capacity for OBS was calculated to be 362.4⯵mol/g according to Langmuir fitting. Electrostatic, π-π and hydrogen bonding interactions were involved in OBS adsorption, and the quaternary N in Fe3O4/rGO was a key adsorption site. The efficiency of the utilization of free radicals generated in Fenton-like and persulfate (PS) systems increased with the increase of OBS adsorbed onto the Fe3O4/rGO, while the increase of OBS amount adsorbed on Fe3O4/rGO would casue a slow OBS removal in the adsorption-degradation process due to the slow adsorption process. The Fenton-like oxidation was more efficient for OBS removal than PS oxidation. The spent Fe3O4/rGO was able to be reused in the Fenton-like system at least ten times, while the OBS removal in the PS reaction system was reduced to 47.8 % after six reuse cycles.