Metal nanostructures in polymeric matrices for optical detection and removal of heavy metal ions, pesticides and dyes from water.

Water pollutants such as heavy metal ions, pesticides, and dyes pose a worldwide issue. Their presence in water resources interferes with the normal growth mechanisms of living beings and causes long or short-term diseases. For this reason, research continuously tends to develop innovative, selective, and efficient processes or technologies to detect and remove pollutants from water. This review provides an up-to-date overview on metal nanoparticles loaded in polymeric matrices, such as hydrogels and membranes, and employed as optical sensors and as removing materials for water pollutants. The synthetic pathways of nanomaterials loading into polymeric matrices have been analyzed, particularly focusing on noble metal nanoparticles, noble metal nanoclusters, and metal oxide nanoparticles. Moreover, the sensing properties of modified matrices towards water pollutants have been discussed in addition to the interaction mechanisms between the sensors and the toxic compounds. The last part of the review has been devoted to illustrating the separation mechanism and removal performance of membranes loaded with nanomaterials in the treatment and purification of water streams from different contaminants (heavy metals, dyes and pesticides).

Study on UF PES Membranes Spray-Coated with Polymerizable Bicontinuous Microemulsion Materials for Low-Fouling Behavior.

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.

Polymeric Membranes Doped with Halloysite Nanotubes Imaged using Proton Microbeam Microscopy.

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.

Cellulose acetate membranes loaded with combinations of tetraphenylporphyrin, graphene oxide and Pluronic F-127 as responsive materials with antibacterial photodynamic activity.

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.

Fabrication of a Zircon Microfiltration Membrane for Culture Medium Sterilization.

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.

In Situ Application of Anti-Fouling Solutions on a Mosaic of the Archaeological Park of Ostia Antica.

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.

Tamisolve® NxG as an Alternative Non-Toxic Solvent for the Preparation of Porous Poly (Vinylidene Fluoride) Membranes.

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.

Pervaporation, Vapour Permeation and Membrane Distillation: From Membrane Fabrication to Application.

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. [...].

Exploring the Effect of Iron Metal-Organic Framework Particles in Polylactic Acid Membranes for the Azeotropic Separation of Organic/Organic Mixtures by Pervaporation.

A microporous carboxylate metal-organic framework MIL-100 Fe was prepared as submicron particles by microwave-assisted hydrothermal synthesis (Fe-MOF-MW). This product was explored, for the first time, for the preparation of polylactic acid (PLA) mixed matrix membranes. The produced MOF was characterised by powder X-ray diffraction (PXRD), environmental scanning electron microscopy (ESEM) as well as by thermogravimetric analysis (TGA) and nitrogen adsorption/desorption. The effect of different Fe-MOF-MW concentrations (0.1 and 0.5 wt%) on the membrane properties and performance were evaluated. These membranes were used in the pervaporation process for the separation of methanol/methyl tert-butyl-ether mixtures at the azeotropic point. The influence of the feed temperature and vacuum pressure on the membrane performance was evaluated and the results were compared with PLA pristine membranes. Moreover, the produced membranes have been characterised in terms of morphology, MOF dispersion in the polymeric membrane matrix, wettability, thickness, mechanical resistance and swelling propensity. The presence of Fe-MOF-MW was found to have a beneficial effect in improving the selectivity of mixed matrix membranes towards methanol at both concentrations. The highest selectivity was obtained for the PLA membranes embedded with 0.5 wt% of Fe-MOF-MW and tested at the temperature of 25 °C and vacuum pressure of 0.09 mbar.

A systematic review on carbohydrate biopolymers for adsorptive remediation of copper ions from aqueous environments-Part B: Isotherms, thermokinetics and reusability.

The presence of copper in aquatic environment is a serious threat for human health and ecosystem conservation. Adsorption is a powerful, operable and economic method for remediation of copper ions from aqueous phase. Carbohydrate biopolymers have emerged as promising, effective and environmental-friendly adsorbents for copper remediation. In part A of this review, different types of carbohydrate biopolymer adsorbents were surveyed focusing on prevalent and novel synthesis and modification methods. In current work (part B of the review), isothermal, thermodynamic and kinetic aspects of the copper adsorption by carbohydrate-based adsorbents as well as the regeneration and reusability of the biopolymer adsorbents are overviewed. Adsorption capacity, time required for equilibrium (adsorption rate), thermal-sensitivity of the adsorption, favorability extent, and sustainability of the adsorbents and adsorption processes are valuable and useful outcomes, resulted from the thermokinetic and reusability investigations. Such considerations are critical for the process design and scale up regarding technical, economical and sustainability of the adsorption process.

Viscosity Modification of Polymerizable Bicontinuous Microemulsion by Controlled Radical Polymerization for Membrane Coating Applications.

Membrane modification is becoming ever more relevant for mitigating fouling phenomena within wastewater treatment applications. Past research included a novel low-fouling coating using polymerizable bicontinuous microemulsion (PBM) induced by UV-LED polymerization. This additional cover layer deteriorated the filtration capacity significantly, potentially due to the observed high pore intrusion of the liquid PBM prior to the casting process. Therefore, this work addressed an innovative experimental protocol for controlling the viscosity of polymerizable bicontinuous microemulsions (PBM) before casting on commercial ultrafiltration (UF) membranes. Prior to the coating procedure, the PBM viscosity modulation was carried out by controlled radical polymerization (CRP). The regulation was conducted by introducing the radical inhibitor 2,2,6,6-tetramethylpiperidine 1-oxyl after a certain time (CRP time). The ensuing controlled radical polymerized PBM (CRP-PBM) showed a higher viscosity than the original unpolymerized PBM, as confirmed by rheological measurements. Nevertheless, the resulting CRP-PBM-cast membranes had a lower permeability in water filtration experiments despite a higher viscosity and potentially lower pore intrusion. This result is due to different polymeric structures of the differently polymerized PBM, as confirmed by solid-state nuclear magnetic resonance (NMR) investigations. The findings can be useful for future developments in the membrane science field for production of specific membrane-coating layers for diverse applications.

Polyvinylidene Fluoride-Graphene Oxide Membranes for Dye Removal under Visible Light Irradiation.

In this study, polyvinylidene fluoride (PVDF)-graphene oxide (GO) membranes were obtained by employing triethyl phosphate (TEP) as a solvent. GO nanosheets were prepared and characterized in terms of scanning and transmission electron microscopy (SEM and TEM, respectively), atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), chemical analysis and inductively coupled plasma mass spectroscopy (ICP). Two different phase inversion techniques, Non-Solvent Induced Phase Separation (NIPS) and Vapour-Induced Phase Separation (VIPS)/NIPS, were applied to study the effect of fabrication procedure on the membrane structure and properties. Membranes were characterized by SEM, AFM, pore size, porosity, contact angle and mechanical tests, and finally tested for photocatalytic methylene blue (MB+) degradation under visible light irradiation. The effect of different pH values of dye aqueous solutions on the photocatalytic efficiency was investigated. Finally, the influence of NaCl salt on the MB+ photodegradation process was also evaluated.

A systematic review on carbohydrate biopolymers for adsorptive remediation of copper ions from aqueous environments-part A: Classification and modification strategies.

Copper is one of the most toxic heavy metals which must be eliminated from aqueous environments, according to the environmental standards. Carbohydrate biopolymers are promising candidates for synthesizing copper-adsorbent composites. It is due to unique properties such as having potential adsorptive functional sites, availability, biocompatibility and biodegradability, formability, blending capacity, and reusability. Different types of copper-adsorbent carbohydrate biopolymers like chitosan and cellulose with particular focus on the synthesizing and modification approaches have been tackled in this review. Composites, functionality and morphological aspects of the biopolymer adsorbents have also been surveyed. Further progress in the fabrication and application of biopolymer adsorbents would be achievable with special attention to some critical challenges such as the process economy, copolymer and/or (nano) additive selection, and the physicochemical stability of the biopolymer composites in aqueous media.

Membrane Bioreactor-Treated Domestic Wastewater for Sustainable Reuse in the Lake Victoria Region.

Lake Victoria is a shared water resource between Kenya, Uganda, and Tanzania, which is the second largest freshwater lake in the world. It has long since suffered from the consequences of overexploitation of its resources, mainly fish stocks, and increasingly high pollution. The closure of 58% of the fish processing plants (FPPs) is attributed to the declining fish stocks due to overfishing and pollution in particular. The installation and operation of a pilot membrane bioreactor (MBR) in Kisumu, Kenya, adopts an integrated approach by providing an integral, sustainable, cost-effective, and robust solution for water sanitation, which also meets the demand for clean water in the fish processing industry, aquaculture, and irrigation. The innovative system comprises a pilot MBR coupled with a recirculation aquaculture system (RAS). The RAS is able to recirculate 90% to 95% of its water volume; only the water loss through evaporation and drum filter back flushing has to be replaced. To compensate for this water deficit, the MBR treats domestic wastewater for further reuse. Additionally, excess purified water is used for irrigating a variety of local vegetables and could also be used in FPPs. The pilot-scale MBR plant with around 6 m2 submerged commercial polyethersulfone (PES) membranes provides treated water in basic agreement with Food and Agriculture Organization (FAO) standards for irrigation and aquaculture, showing no adverse effects on tilapia fingerlings production. A novel membrane module with a low-fouling coating is operating stably but has not yet shown improved performance compared to the commercial one. Integr Environ Assess Manag 2020;16:942-954. © 2020 The Authors. Integrated Environmental Assessment and Management published by Wiley Periodicals LLC on behalf of Society of Environmental Toxicology & Chemistry (SETAC).

Innovative Poly (Vinylidene Fluoride) (PVDF) Electrospun Nanofiber Membrane Preparation Using DMSO as a Low Toxicity Solvent.

Electrospinning is an emerging technique for the preparation of electrospun fiber membranes (ENMs), and a very promising one on the basis of the high-yield and the scalability of the process according to a process intensification strategy. Most of the research reported in the literature has been focused on the preparation of poly (vinylidene fluoride) (PVDF) ENMs by using N,N- dimethylformamide (DMF) as a solvent, which is considered a mutagenic and cancerogenic substance. Hence, the possibility of using alternative solvents represents an interesting approach to investigate. In this work, we explored the use of dimethyl sulfoxide (DMSO) as a low toxicity solvent in a mixture with acetone for the preparation of PVDF-ENMs. As a first step, a solubility study of the polymer, PVDF 6012 Solef®, in several DMSO/acetone mixtures was carried out, and then, different operating conditions (e.g., applied voltage and needle to collector plate distance) for the successful electrospinning of the ENMs were evaluated. The study provided evidence of the crucial role of solution conductivity in the electrospinning phase and the thermal post-treatment. The prepared ENMs were characterized by evaluating the morphology (by SEM), pore-size, porosity, surface properties, and performance in terms of water permeability. The obtained results showed the possibility of producing ENMs in a more sustainable way, with a pore size in the range of 0.2-0.8 µm, high porosity (above 80%), and water flux in the range of 11.000-38.000 L/m2·h·bar.

Chemical and bio-chemical reactions assisted by pervaporation technology.

Since several decades ago, the application of pervaporation (PV) technology has been mainly aimed at the separation of different types of water-organic, organic-water and organic-organic mixtures, reaching its large-scale application in industry for the dehydration of organics. Today, the versatility and high selectivity toward specific compounds have led its consideration to other types of application such as the assisted chemical and bio-chemical reactions. The focus of this review is to provide a compelling overview on the recent developments of PV combined with chemical and bio-chemical reactions. After a general introduction of PV and its theoretical background, particular emphasis is given to the results obtained in the field for different reactions considered, identifying the key features and weak points of PV in such particular applications. Furthermore, future trends and perspectives are also addressed according to the latest literature reports.

Membrane-Based Clarification and Fractionation of Red Wine Lees Aqueous Extracts.

Polyvinylidenefluoride (PVDF) hollow fiber membranes prepared in laboratory through the inversion phase method were characterized and used to clarify an aqueous extract from red wine lees. Steady-state permeate fluxes of 53 kg/m2h were obtained in the treatment of the aqueous extract in selected operating conditions. Suspended solids were completely retained by the hollow fiber membranes while bioactive compounds, including polyphenols, anthocyanins, and resveratrol were recovered in the permeate stream. The clarified stream was then fractionated by nanofiltration (NF). Three different commercial membranes, in flat-sheet configuration (NP010 and NP030 from Microdyn-Nadir, MPF36 from Koch Membrane Systems), were selected and tested for their productivity and selectivity towards sugars and bioactive compounds, including phenolic compounds, anthocyanins, and resveratrol. All selected membranes showed high retention towards anthocyanins (higher than 93%). Therefore, they were considered suitable to concentrate anthocyanins from clarified wine lees extracts at low temperature. On the other hand, NF permeate streams resulted enriched in phenolic compounds and resveratrol. Among the selected membranes, the MPF36 exhibited the lowest retention towards resveratrol (10%) and polyphenols (26.3%) and the best separation factor between these compounds and anthocyanins.

New Polymeric Films with Antibacterial Activity Obtained by UV-induced Copolymerization of Acryloyloxyalkyltriethylammonium Salts with 2-Hydroethyl Methacrylate.

New polymeric films with antibacterial activity have been prepared, by simple UV-induced copolymerization of readily available ω-(acryloyloxy)-N,N,N-triethylalcan-1-aminium bromides (or acryloyloxyalkyltriethylammonium bromides, AATEABs) with commercially available 2-hydroethyl methacrylate (HEMA), at different relative amounts. In particular, the antibacterial activity of polymeric films derived from 11-(acryloyloxy)-N,N,N-triethylundecan-1-aminium bromide (or acryloyloxyundecyltriethylammonium bromide, AUTEAB; bearing a C-11 alkyl chain linker between the acrylate polymerization function and the quaternary ammonium moiety) and 12-(acryloyloxy)-N,N,N-triethyldodecan-1-aminium bromide (or acryloyldodecyltriethylammonium bromide, ADTEB, bearing a C-12 alkyl chain linker) has been assessed against Gram-negative Escherichia Coli and Gram-positive Staphylococcus aureus cells. The results obtained have shown a clear concentration-dependent activity against both bacterial strains, the films obtained from homopolymerization of pure AUTEAB and ADTEAB being the most effective. Moreover, ADTEAB-based films showed a higher antibacterial activity with respect to the AUTEAB-based ones. Interestingly, however, both types of films presented a significant activity not only toward Gram-positive S. aureus, but also toward Gram-negative E. Coli cells.

The language profile of progressive supranuclear palsy.

A progressive speech/language disorder, such as the non fluent/agrammatic variant of primary progressive aphasia and progressive apraxia of speech, can be due to neuropathologically verified Progressive Supranuclear Palsy (PSP). The prevalence of linguistic deficits and the linguistic profile in PSP patients who present primarily with a movement disorder is unknown. In the present study, we investigated speech and language performance in a sample of clinically diagnosed PSP patients using a comprehensive language battery, including, besides traditional language tests, a detailed analysis of connected speech (picture description task assessing 26 linguistic features). The aim was to identify the most affected linguistic levels in seventeen PSP with a movement disorder presentation, compared to 21 patients with Parkinson's disease and 27 healthy controls. Machine learning methods were used to detect the most relevant language tests and linguistic features characterizing the language profile of PSP patients. Our results indicate that even non-clinically aphasic PSP patients have subtle language deficits, in particular involving the lexical-semantic and discourse levels. Patients with the Richardson's syndrome showed a lower performance in the word comprehension task with respect to the other PSP phenotypes with predominant frontal presentation, parkinsonism and progressive gait freezing. The present findings support the usefulness of a detailed language assessment in all patients in the PSP spectrum.

Preparation and Characterization of TiO2-PVDF/PMMA Blend Membranes Using an Alternative Non-Toxic Solvent for UF/MF and Photocatalytic Application.

The approach of the present work is based on the use of poly (methylmethacrylate) (PMMA) polymer, which is compatible with PVDF and TiO2 nanoparticles in casting solutions, for the preparation of nano-composites membranes using a safer and more compatible solvent. TiO2 embedded poly (vinylidene fluoride) (PVDF)/PMMA photocatalytic membranes were prepared by phase inversion method. A non-solvent induced phase separation (NIPS) coupled with vapor induced phase separation (VIPS) was used to fabricate flat-sheet membranes using a dope solution consisting of PMMA, PVDF, TiO2, and triethyl phosphate (TEP) as an alternative non-toxic solvent. Membrane morphology was examined by scanning electron microscopy (SEM). Backscatter electron detector (BSD) mapping was used to monitor the inter-dispersion of TiO2 in the membrane surface and matrix. The effects of polymer concentration, evaporation time, additives and catalyst amount on the membrane morphology and properties were investigated. Tests on photocatalytic degradation of methylene blue (MB) were also carried out using the membranes entrapped with different concentrations of TiO2. The results of this study showed that nearly 99% MB removal can be easily achieved by photocatalysis using TiO2 immobilized on the membrane matrix. Moreover, it was observed that the quantity of TiO2 plays a significant role in the dye removal.