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During the production and laying phases of hot-mixing asphalt (HMA), various volatile organic compounds (VOCs) and noxious gases such as H2S are released into the atmosphere. These emissions are a serious environmental problem, a risk to human health, and expose workers and residents to unfriendly odours. The aim of this study was the development of a fast and sensitive analytical method to detect the H2S emitted from hot bituminous binder that is generally used in the various stages of asphalt production, processing, handling and during road construction. The method consisted in the analysis of evolved H2S from a flask with molten bitumen, using nitrogen as a carrier gas to lead the volatile compounds into a residual gas analyser equipped with a quadrupole mass spectrometer. The analysis was performed following the H2S-specific signals at m/z 33 (HS+) and at m/z 34 (H2S+) in real time, directly on the sample without laborious and expensive pre-treatments and with short response times (<6 s). Calibration with a standard mixture of 1000 ppm of H2S in nitrogen allows semi-quantitative H2S detection. The sensitivity and rapidity of the method were evaluated by quenching the release of sulphur compounds with commercial odour-suppressing agents. Upon addition of 0.1% of additive in two minutes, the H2S signal drops about 80% in two minutes, confirming the good response of the method, even with a very complex matrix.
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Conductive polymers, such as polyaniline (PANI), have interesting applications, ranging from flexible electronics, energy storage devices, sensors, antistatic or anticorrosion coatings, etc. However, the full exploitation of conductive polymers still poses a challenge due to their low processability. The use of compatible stabilizers to obtain dispersible and stable colloids is among the possible solutions to overcome such drawbacks. In this work, potato starch was used as a steric stabilizer for the preparation of colloidal polyaniline (emeraldine salt, ES)/starch composites by exploiting the oxidative polymerization of aniline in aqueous solutions with various starch-to-aniline ratios. The polyaniline/starch bio-composites were subjected to structural, spectroscopic, thermal, morphological, and electrochemical analyses. The samples were then tested for their dispersibility/solubility in a range of organic solvents. The results demonstrated the formation of PANI/starch biocomposites with a smaller average size than starch particles, showing improved aqueous dispersion and enhanced solubility in organic solvents. With respect to previously reported PANI-EB (emeraldine base)/starch composites, the novel colloids displayed a lower overall crystallinity, but the conductive nature of PANI-ES enhanced its electrochemical properties, resulting in richer redox chemistry, particularly evident in its oxidation behavior, as observed through cyclic voltammetry. Finally, as proof of the improved processability, the colloids were successfully integrated into a thin polyether sulfone (PES) membrane.
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The low-fouling propensity of commercially available polyethersulfone (PES) membranes was studied after modification of the membrane surface via coating with polymerizable bicontinuous microemulsion (PBM) materials. The PBM coating was polymerized within 1 min using ultraviolet (UV) light exposure. It was detected on the PES membrane surface via attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy. The PBM coating led to an average 10% increase in the hydrophilicity of the PES membrane surface and an increase in total organic content (TOC) removal by more than 15%. Flux-step tests were conducted with model foulant comprising 100 mg L-1 humic acid (HA) solution to detect the onset of critical fouling, characterized by a rapid and substantial increase in TMP, and to compare the fouling propensity of commercially available PES membranes with PBM-coated membranes. The critical flux was found to be about 40% higher for PBM spray-coated membrane and 20% lower for PBM casting-coated membrane than the commercial PES membrane. This demonstrates the performance advantages of the thin PBM layer spray-coated on PES membrane compared to the thick casting-coated PBM layer. The study showcases the potential of PBM spray-coated membranes over commercial PES membranes for use in membrane bioreactors (MBR) for wastewater treatment systems with reduced maintenance over longer operation periods.
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Polymeric membranes are useful tools for water filtration processes, with their performance strongly dependent on the presence of hydrophilic dopants. In this study, polyaniline (PANI)-capped aluminosilicate (halloysite) nanotubes (HNTs) are dispersed into polyether sulfone (PES), with concentrations ranging from 0.5 to 1.5 wt%, to modify the properties of the PES membrane. Both undoped and HNT-doped PES membranes are investigated in terms of wettability (static and time-dependent contact angle), permeance, mechanical resistance, and morphology (using scanning electron microscopy (SEM)). The higher water permeance observed for the PES membranes incorporating PANI-capped HNTs is, finally, assessed and discussed vis-à-vis the real distribution of HNTs. Indeed, the imaging and characterization in terms of composition, spatial arrangement, and counting of HNTs embedded within the polymeric matrix are demonstrated using non-destructive Micro Particle Induced X-ray Emission (µ-PIXE) and Scanning Transmission Ion Microscopy (STIM) techniques. This approach not only exhibits the unique ability to detect/highlight the distribution of HNTs incorporated throughout the whole thickness of polymer membranes and provide volumetric morphological information consistent with SEM imaging, but also overcomes the limits of the most common analytical techniques exploiting electron probes. These aspects are comprehensively discussed in terms of practical analysis advantages.
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The development of polymeric fabrics with photoinduced antibacterial activity is important for different emerging applications, ranging from materials for medical and clinical practices to disinfection of objects for public use. In this work we prepared a series of cellulose acetate membranes, by means of phase inversion technique, introducing different additives in the starting polymeric solution. The loading of 5,10,15,20-tetraphenylporphyrin (TPP), a known photosensitizer, was considered to impart antibacterial photodynamic properties to the produced membranes. Besides, the addition of a surfactant (Pluronic F-127) allowed to modify the morphology of the membranes whereas the use of graphene oxide (GO) enabled further photo-activated antibacterial activity. The three additives were tested in various concentrations and in different combinations in order to carefully explore the effects of their mixing on the final photophysical and photodynamic properties. A complete structural/morphologycal characterization of the produced membranes has been performed, together with a detailed photophysical study of the TPP-containing samples, including absorption and emission features, excited state lifetime, singlet oxygen production, and confocal analysis. Their antibacterial activity has been assessed in vitro against S. aureus and E. coli, and the results demonstrated excellent bacterial inactivation for the membranes containing a combination of the three additives, revealing also a non-innocent role of the membrane porous structure in the final antibacterial capacity.
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Ionotropic gelation (IG) is a highly attractive method for the synthesis of natural water-soluble polymeric nanoparticles (NPs) and sub-micron particles (sMP) due to its relatively simple procedure and the absence of organic solvents. The method involves the electrostatic interaction between two ionic species of opposite charge. Although it is well studied at the laboratory scale, the difficulty to achieve size control in conventional bench-top process is actually a critical aspect of the technology. The aim of this work is to study the membrane dispersion technology in combination with IG as a suitable scalable method for the production of chitosan sub-micron particles (CS-sMPs). The two phases, one containing chitosan (CS) and the other containing sodium tripolyphosphate (TPP), were put in contact using a tubular hydrophobic glass membrane with a pore diameter of 1 µm. TPP (dispersed phase) was permeated through the membrane pores into the lumen side along which the CS solution (the continuous phase) flowed in batch recirculation or continuous single-pass operation mode. The influence of chemical variables (i.e. pH, concentration and mass ratio of polyelectrolyte species, emulsifier) and fluid-dynamic parameters (i.e. polyelectrolyte solution flow rate and their relative mass ratio) was studied to precisely tune the size of CS-Ps.
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The major challenge for membrane distillation (MD) is the membrane wetting resistance induced by pollutants in the feed solution. The proposed solution for this issue was to fabricate membranes with hydrophobic properties. Hydrophobic electrospun poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) nanofiber membranes were produced for brine treatment using the direct-contact membrane distillation (DCMD) technique. These nanofiber membranes were prepared from three different polymeric solution compositions to study the effect of solvent composition on the electrospinning process. Furthermore, the effect of the polymer concentration was investigated by preparing polymeric solutions with three different polymer percentages: 6, 8, and 10%. All of the nanofiber membranes obtained from electrospinning were post-treated at varying temperatures. The effects of thickness, porosity, pore size, and liquid entry pressure (LEP) were studied. The hydrophobicity was determined using contact angle measurements, which were investigated using optical contact angle goniometry. The crystallinity and thermal properties were studied using DSC and XRD, while the functional groups were studied using FTIR. The morphological study was performed with AMF and described the roughness of nanofiber membranes. Finally, all of the nanofiber membranes had enough of a hydrophobic nature to be used in DCMD. A PVDF membrane filter disc and all nanofiber membranes were applied in DCMD to treat brine water. The resulting water flux and permeate water quality were compared, and it was discovered that all of the produced nanofiber membranes showed good behavior with varying water flux, but the salt rejection was greater than 90%. A membrane prepared from DMF/acetone 5-5 with 10% PVDF-HFP provided the perfect performance, with an average water flux of 44 kg.m-2.h-1 and salt rejection of 99.8%.
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Multilayer ceramic membranes to be used for bacteria removal by filtration were prepared from ceramic materials. They consist of a macro-porous carrier, an intermediate layer and a thin separation layer at the top. Tubular and flat disc supports were prepared from silica sand and calcite (natural raw materials), using extrusion and uniaxial pressing methods, respectively. Making use of the slip casting technique, the silica sand intermediate layer and the zircon top-layer were deposited on the supports, in this order. The particle size and the sintering temperature for each layer were optimized to achieve a suitable pore size for the deposition of the next layer. Morphology, microstructures, pore characteristics, strength and permeability were also studied. Filtration tests were conducted to optimize the permeation performance of the membrane. Experimental results show that the total porosity and average pore size of the porous ceramic supports sintered at different temperatures within the range (1150-1300 °C), and lie in the ranges of 44-52% and 5-30 µm, respectively. For the ZrSiO4 top-layer, after firing at 1190 °C, a typical average pore size of about 0.3 µm and a thickness of about 70 µm were measured, while water permeability is estimated to a value of 440 lh-1m-2bar-1. Finally, the optimized membranes were tested in the sterilization of a culture medium. Filtration results show the efficiency of the zircon-deposited membranes for bacteria removal; indeed, the growth medium was found to be free of all microorganisms.
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Membrane capacitive deionization (MCDI) has shown many advances, however, its performance in combination with other treatment technologies has not been widely reported. In this study, a pilot-scale low-pressure reverse osmosis (LPRO) (FilmTec™ XLE-2540) with MCDI (CapDI© C17, Voltea) was developed and tested as a promising modular desalination system. The systems were evaluated individually at different salinities and tested together as a modular system. The study focused in the comparison to conventional seawater reverse osmosis (SWRO) (FilmTec™ SW30-2540) at pilot-scale and in theory using the software Water Application Value Engine (WAVE, DuPont™), including a cost evaluation of the systems. Pilot tests were carried out in Can Gio, a riverine estuary region in South Vietnam, which is affected by progressive salinization (TDS ≈ 1-25 g/L). Drinking water quality (TDS < 600 mg/L) was achieved with a specific energy consumption (SEC) of 5.2 kWh/m³. Additionally, fouling mitigation was investigated for the ultrafiltration (UF) pre-treatment by periodic hydraulic and chemical enhanced backwashing. While the SWRO had a slightly lower SEC of 5.0 kWh/m³, WAVE calculations showed that lowering the SEC to 3.6 kWh/m³ is possible by improving the LPRO pump design and an optimization of the MCDI operation.
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Purificação da Água , Vietnã , Osmose , Membranas Artificiais , Água do MarRESUMO
Fluoropolymer membranes are applied in membrane operations such as membrane distillation and membrane crystallization where hydrophobic porous membranes act as a physical barrier separating two phases. Due to their hydrophobic nature, only gaseous molecules are allowed to pass through the membrane and are collected on the permeate side, while the aqueous solution cannot penetrate. However, these two processes suffer problems such as membrane wetting, fouling or scaling. Membrane wetting is a common and undesired phenomenon, which is caused by the loss of hydrophobicity of the porous membrane employed. This greatly affects the mass transfer efficiency and separation efficiency. Simultaneously, membrane fouling occurs, along with membrane wetting and scaling, which greatly reduces the lifespan of the membranes. Therefore, strategies to improve the hydrophobicity of membranes have been widely investigated by researchers. In this direction, hydrophobic fluoropolymer membrane materials are employed more and more for membrane distillation and membrane crystallization thanks to their high chemical and thermal resistance. This paper summarizes different preparation methods of these fluoropolymer membrane, such as non-solvent-induced phase separation (NIPS), thermally-induced phase separation (TIPS), vapor-induced phase separation (VIPS), etc. Hydrophobic modification methods, including surface coating, surface grafting and blending, etc., are also introduced. Moreover, the research advances on the application of less toxic solvents for preparing these membranes are herein reviewed. This review aims to provide guidance to researchers for their future membrane development in membrane distillation and membrane crystallization, using fluoropolymer materials.
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Biodegradation is among the most common issues affecting Cultural Heritage stone materials in outdoor environments. In recent years, the application of chemical agents with biocidal activity has been the most usual practice when dealing with biofilm removal. In outdoor environments, the use of these biocides is not effective enough, since the materials are constantly exposed to environmental agents and atmospheric pollutants. Thus, it becomes necessary to protect the surface of Cultural Heritage works with antimicrobial coatings to either prevent or at least limit future colonization. In this study, innovative biocides-both natural and synthetic-were applied on a Roman mosaic located in the Archaeological Park of Ostia Antica to compare their effectiveness in removing the biological degradation affecting it. In addition, an antimicrobial coating called "SI-QUAT" was applied and analyzed in situ. SI-QUAT has recently entered the market for its prevention activity against biocolonization. The biocidal activity of these products was tested and monitored using different analytical portable instruments, such as the multispectral system, the spectrocolorimeter, and the bioluminometer. The analyses showed that promising results can be obtained using the combination of the biocide and the protective effect of Preventol® RI50 and SI-QUAT.
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In this work, innovative graphene oxide-doped waterproofing bituminous membranes, also called roof bituminous membranes, were prepared and characterized in terms of physicochemical and vapor transport properties. The results showed that the introduction of a small amount of GO increased the mechanical resistance of the doped membranes compared to the native one. Moreover, the addition of the GO leads to a remarkable chemical stability of the membranes when exposed to UV radiation and high temperatures. Furthermore, a decrease in water vapor permeation was observed when GO was present in the membrane matrix compared to native bituminous membranes, demonstrating that an addition of GO can boost the waterproofing properties of these bituminous membranes.
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Using an environmentally friendly approach for eliminating methylene blue from an aqueous solution, the authors developed a unique electrospun nanofiber membrane made of a combination of polyethersulfone and hydroxypropyl cellulose (PES/HPC). SEM results confirmed the formation of a uniformly sized nanofiber membrane with an ultrathin diameter of 168.5 nm (for PES/HPC) and 261.5 nm (for pristine PES), which can be correlated by observing the absorption peaks in FTIR spectra and their amorphous/crystalline phases in the XRD pattern. Additionally, TGA analysis indicated that the addition of HPC plays a role in modulating their thermal stability. Moreover, the blended nanofiber membrane exhibited better mechanical strength and good hydrophilicity (measured by the contact angle). The highest adsorption capacity was achieved at a neutral pH under room temperature (259.74 mg/g), and the pseudo-second-order model was found to be accurate. In accordance with the Langmuir fitted model and MB adsorption data, it was revealed that the adsorption process occurred in a monolayer form on the membrane surface. The adsorption capacity of the MB was affected by the presence of various concentrations of NaCl (0.1-0.5 M). The satisfactory reusability of the PES/HPC nanofiber membrane was revealed for up to five cycles. According to the mechanism given for the adsorption process, the electrostatic attraction was shown to be the most dominant in increasing the adsorption capacity. Based on these findings, it can be concluded that this unique membrane may be used for wastewater treatment operations with high efficiency and performance.
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In this work, Eucommia ulmoides leaf extract (EUOLstabilized silver nanoparticles (EUOL@AgNPs) incorporated sulfonated polyether sulfone (SPES)/polyethersulfone (PES) electrospun nanofiber membranes (SP ENMs) were prepared by electrospinning, and they were studied for the removal of lead (Pb(II)) and cadmium (Cd(II)) ions from aqueous solutions. The SP ENMs with various EUOL@AgNPs loadings were characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscope, thermo-gravimetric analysis (TGA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and contact angle (CA) measurements. The adsorption studies showed that the adsorption of Cd(II) and Pb(II) was rapid, achieved equilibrium within 40 min and 60 min, respectively and fitted with non-linear pseudo-second-order (PSO) kinetics model. For Cd(II) and Pb(II), the Freundlich model described the adsorption isotherm better than the Langmuir isotherm model. The maximum adsorption capacity for Cd(II) and Pb(II) was 625 and 370.37 mg g-1 respectively at neutral pH. Coexisting anions of fluoride, chloride, and nitrate had a negligible influence on Cd(II) removal than the Pb(II). On the other hand, the presence of silicate and phosphate considerably affected Cd(II) and Pb(II) adsorption. The recyclability, regeneration, and reusability of the fabricated EUOL@AgNPs-SP ENMs were studied and they retained their high adsorption capacity up to five cycles. The DFT measurements revealed that SP-5 ENMs exhibited the highest adsorption selectivity for Cd(II) and the measured binding energies for Cd(II), Pb(II), are 219.35 and 206.26 kcal mol-1, respectively. The developed ENM adsorbent may find application for the removal of heavy metals from water.
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Nanopartículas Metálicas , Metais Pesados , Nanofibras , Poluentes Químicos da Água , Adsorção , Alcanossulfonatos , Cádmio/análise , Concentração de Íons de Hidrogênio , Cinética , Chumbo , Polímeros , Prata/análise , Sulfonas , Água , Poluentes Químicos da Água/análiseRESUMO
The purification of phycocyanin (PC) from Spirulina generally involves a combination of different techniques. Here, we report the results on PC yields from a combined aqueous extraction-ultrafiltration (UF) process of a strain of Arthrospira maxima cultivated in a farm devoted to producing PC with food-grade purity. Samples optimized from different biomass/solvent ratios were purified by using a polyethersulphone (PES) membrane with a molecular weight cut-off (MWCO) of 20 kDa. The UF system was operated at 2.0 ± 0.1 bar and at 24 ± 2 °C up to a volume concentration factor (VCF) of 5. A diafiltration (DF) process was conducted after UF in order to increase the PC recovery in the retentate. Samples were collected during both UF and DF processes in order to evaluate membrane productivity and PC purity. The average permeate fluxes of about 14.4 L/m2h were measured in the selected operating conditions and more than 96% of PC was rejected by the UF membrane independently ofthe extraction yields and times. The concentration of PC in the final retentate was 1.17 mg/mL; this confirmed the observed rejection and the final VCF of the process (about 5-fold when compared to the concentration of PC in the crude extract). In addition, the combination of UF and diafiltration allowed the removal of about 91.7% of the DNA from the crude extract, thereby improving the purity of the phycocyanin in the retentate fraction.
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In the current work, a Gum, Arabic-modified Graphene (GGA), has been synthesized via a facile green method and employed for the first time as an additive for enhancement of the PPSU ultrafiltration membrane properties. A series of PPSU membranes containing very low (0-0.25) wt.% GGA were prepared, and their chemical structure and morphology were comprehensively investigated through atomic force microscopy (AFM), Fourier transforms infrared spectroscopy (FTIR), X-ray diffraction (XRD), and field emission scanning electron microscopy (FESEM). Besides, thermogravimetric analysis (TGA) was harnessed to measure thermal characteristics, while surface hydrophilicity was determined by the contact angle. The PPSU-GGA membrane performance was assessed through volumetric flux, solute flux, and retention of sodium alginate solution as an organic polysaccharide model. Results demonstrated that GGA structure had been successfully synthesized as confirmed XRD patterns. Besides, all membranes prepared using low GGA content could impart enhanced hydrophilic nature and permeation characteristics compared to pristine PPSU membranes. Moreover, greater thermal stability, surface roughness, and a noticeable decline in the mean pore size of the membrane were obtained.
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Tamisolve® NxG, a well-known non-toxic solvent, was used for poly(vinylidene fluoride) (PVDF) membranes preparation via a non-solvent-induced phase separation (NIPS) procedure with water as a coagulation bath. Preliminary investigations, related to the study of the physical/chemical properties of the solvent, the solubility parameters, the gel transition temperature and the viscosity of the polymer-solvent system, confirmed the power of the solvent to solubilize PVDF polymer for membranes preparation. The role of polyvinylpyrrolidone (PVP) and/or poly(ethylene glycol) (PEG), as pore former agents in the dope solution, was studied along with different polymer concentrations (10 wt%, 15 wt% and 18 wt%). The produced membranes were then characterized in terms of morphology, thickness, porosity, contact angle, atomic force microscopy (AFM) and infrared spectroscopy (ATR-FTIR). Pore size measurements, pore size distribution and water permeability (PWP) tests placed the developed membranes in the ultrafiltration (UF) and microfiltration (MF) range. Finally, PVDF membrane performances were investigated in terms of rejection (%) and permeability recovery ratio (PRR) using methylene blue (MB) in water solution to assess their potential application in separation and purification processes.
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The aim of this work is the optimization of the operating conditions under which MCM-41-mesoporous material can be incorporated into polyethersulfone (PES)/MCM-41 membranes for nanofiltration (NF) applications. MCM-41 mesoporous material mixed matrix PES membranes have the potential to reduce membrane fouling by organic dye molecules. Process optimization and modeling aim to reduce wasted energy while maintaining high flow during the operation to handle the energy efficiency problems membranes often have. An optimization technique was applied to obtain optimum values for some key parameters in the process to produce a certain amount of flux above the desired values. Response surface methodology (RSM) and analysis of variance (ANOVA) were used as mathematical and statistical analyses to improve the performance of the process on a larger scale. This work investigated the influence of the operating parameters, such as the feed pH values (3-11), MCM-41 content (0-1 wt.%), and the feed dye concentration (10-100 ppm) for each of the two studied dyes, acid black 210 (AB-210) and rose bengal (RB), and their interactions on the PES membrane permeability. The results showed that the PES membrane had the best performance at 64.25 (L·m-2·h-1·bar-1) and 63.16 (L·m-2·h-1·bar-1) for the AB-210 and RB dyes, respectively. An MCM-41 content of nearly 0.8 wt.% in the casting solution, feed dye concentration of 10 ppm for the studied dyes, and feed pH of 3 for the RB dye was found to be the optimal parameters for eliciting the response. The pH had no significant influence on the response for the AB-210 dye, while the pH shows some minor effects on response with the RB dye, and the Pareto chart of the standardized effects on the permeation flux of both dyes using statistically significant at the 5% significance level support these results.
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Various technologies are used for the treatment of arsenic (As) contaminated water, but only a few seem to be suitable for small-scale applications; these are mostly used in rural communities where the access to potable water is the most vulnerable. In this review paper, the salient advantages and most notable challenges of membrane-based technologies for the removal of arsenate As(V) and arsenite As(III) are evaluated and systematically compared to alternative technologies such as e.g. adsorption. A comparison of different scientific papers, case studies and pilot trials is used to discuss the most important aspects when evaluating As mitigation technologies, including the ability to comply with the stringent WHO drinking water guideline limit value of 10 µg/L As and the safe disposal of produced As-laden waste. The use of renewable energies such as solar power in small-scale (<10 m³/day) membrane applications is evaluated. Finally, a conceptual approach for holistic As mitigation is proposed as an important approach to prevent exposure to As by providing a safe water supply.
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Arsênio , Água Potável , Poluentes Químicos da Água , Purificação da Água , Adsorção , Arsênio/análise , Poluentes Químicos da Água/análise , Abastecimento de ÁguaRESUMO
In recent decades, membrane technologies have attracted a lot of interest in operations for highly selective separations. Particularly, pervaporation (PV), vapour permeation (VP) and membrane distillation (MD) represent three membrane processes well-studied and applied at the research level and with a great potential of exploitation in different industrial sectors. [...].