Revisiting Membranes-An Open Access Membrane Science and Technology Journal.

Membranes is celebrating its 13th anniversary this year [...].

Microfluidic paper-based analytical device for the speciation of inorganic nitrogen species.

A microfluidic paper-based analytical device (µPAD) utilizing gas-diffusion separation and solid-phase reduction was developed for the first time for the determination of both ammonium and nitrate, which are the dominant inorganic nitrogen species in environmental waters. The device consists of 3 filter paper layers accommodating the sample, reagent and detection zones. The reagent zone is separated from the detection zone by a semipermeable hydrophobic membrane and acts as a solid-phase reactor where nitrate is reduced to ammonia by Devarda's alloy microparticles, integrated into a µPAD for the first time. The detection zone incorporates the acid-base indicators bromothymol blue (BTB) or nitrazine yellow (NY) and changes colour in two steps. Initially the colour change is caused by ammonia generated by the reaction of ammonium and sodium hydroxide in the sample zone. This colour change is followed by a subsequent colour change as a result of the ammonia produced by the reduction of nitrate by the Devarda's alloy microparticles. The corresponding reflectance value changes are used for the quantification of the two inorganic nitrogen species in the ranges 6.5-100.0 or 2.1-15.0 mg N L-1 for ammonium and 18.2-100.0 or 4.2-15.0 mg N L-1 for nitrate when BTB or NY are used, respectively. Under optimal conditions the limits of quantification of ammonium and nitrate in the case of BTB were determined as 6.5 and 18.2 mg N L-1, respectively, while the corresponding values in the case of NY were found to be 2.1 and 4.2 mg N L-1. The newly developed µPAD was stable for 62 days when stored in a freezer and 1 day at ambient temperature. It was validated with a certified reference material and successfully applied to the determination of ammonium and nitrate in spiked environmental water samples and soil extracts.

A Comprehensive Study on the Effect of Plasticizers on the Characteristics of Polymer Inclusion Membranes (PIMs): Exploring Butyl Stearate as a Promising Alternative.

This study investigated the influence of various plasticizers commonly used in the manufacture of polymer inclusion membranes (PIMs), such as 2-nitrophenyl octyl ether (NPOE), phthalates, adipates, and sebacates on the mechanical, thermal, and transport properties of membranes. Additionally, butyl stearate (BTS), chosen for its non-toxic nature compared to phthalates and its cost-effectiveness relative to adipates and sebacates, was evaluated as a plasticizer in PIMs for the first time. All plasticizers were incorporated in PIMs made of either cellulose triacetate (CTA) or poly(vinyl chloride) (PVC) as the base polymers and the task-specific ionic liquid trioctylmethylammonium thiosalicylate (TOMATS) as the carrier. The plasticizers were found to significantly affect the characteristics of membrane hydrophilicity, mechanical flexibility, and thermal stability. Transport experiments using Hg(II) as a model target ion revealed that, for CTA-based PIMs, the plasticizer did not significantly affect transport efficiency. However, for PVC-based PIMs, BTS exhibited better efficiency when compared to NPOE. These findings highlight the potential of BTS as an attractive alternative to currently used plasticizers in PVC-based PIM formulations.

Determination of N-Acetyl-L-cysteine Ethyl Ester (NACET) by Sequential Injection Analysis.

New sequential injection analysis (SIA) methods with optical sensing for the determination of N-acetyl-L-cysteine ethyl ester (NACET) have been developed and optimized. NACET is a potential drug and antioxidant with advantageous pharmacokinetics. The methods involve the reduction of Cu(II) in its complexes with neocuproine (NCN), bicinchoninic acid (BCA), and bathocuproine disulfonic acid (BCS) to the corresponding chromophoric Cu(I) complexes by the analyte. The absorbance of the Cu(I) complexes with NCN, BCA, and BCS was measured at their maximum absorbance wavelengths of 458, 562, and 483 nm, respectively. The sensing manifold parameters and experimental conditions were optimized for each of the Cu(II) complexes used. Under optimal conditions, the corresponding linear calibration ranges, limits of detection, and sampling rates were 8.0 × 10-6-2.0 × 10-4 mol L-1, 5.5 × 10-6 mol L-1, and 60 h-1 for NCN; 6.0 × 10-6-1.0 × 10-4 mol L-1, 5.2 × 10-6 mol L-1, and 60 h-1 for BCA; and 4.0 × 10-6-1.0 × 10-4 mol L-1, 2.6 × 10-6 mol L-1, and 78 h-1 for BCS. The Cu(II)-BCS complex was found to be best performing in terms of sensitivity and sampling rate. Usual excipients in pharmaceutical preparations did not interfere with NACET analysis.

The determination of zinc using flow injection and continuous flow analysis combined with a polymer inclusion film-coated column: Application to the determination of zinc in alloys and commercial lithium chloride.

A column coated with a polymer inclusion film (PIF) containing Aliquat 336 as carrier cast on glass beads packed in a glass tube is described for the separation, preconcentration, and determination of zinc(II) in flow injection analysis (FIA) and continuous flow analysis (CFA) systems. In the FIA method, 200 µL of a sample solution containing 2 mol/L lithium chloride is injected into a 2 mol/L lithium chloride stream. This converts zinc(II) ion into its anionic chlorocomplexes which are then extracted into the Aliquat 336-based PIF by anion exchange. The extracted zinc(II) is then back-extracted into a stream of 1 mol/L sodium nitrate solution and determined spectrophotometrically using 4-(2-pyridylazo)resorcinol as the color reagent. The limit of detection (LOD, S/N = 2) was determined as 0.017 mg/L. The usability of the PIF-based FIA method was demonstrated by the determination of zinc in alloys. The PIF-coated column was also employed successfully in the CFA determination of zinc(II) as an impurity in commercial lithium chloride samples. For this, 2 mol/L commercial lithium chloride solution was passed through the column for a predetermined time period followed by stripping in a stream of 1 mol/L sodium nitrate solution.

A Modern Computer Application to Model Rare Earth Element Ion Behavior in Adsorptive Membranes and Materials.

The following paper offers a modern REE 1.0 computer application designed to model the behavior of REE ions in adsorptive materials and membranes. The current version of the application is based on several models, such as the Lagergren pseudo-first order, pseudo-second-order and Elovich kinetic models, and the intraparticle diffusion model, the diffusion-chemisorption model, and the Boyd model. The application has been verified on a sample of four different types of adsorptive materials and membranes. The proposed application allowed the analysis of kinetics, but also the mechanisms of the adsorption process, especially those responsible for the rate-determining steps. It was found that Lagergren pseudo-second-order kinetic model was the best-fit model to describe the adsorption behavior of REE ions onto the novel materials and membranes. Other models determined the process of chemisorption was in force for the analyzed cases, and the mechanisms controlling the adsorption processes are diffusion-chemisorption and adsorption is mostly controlled by film diffusion. Additionally, characteristic parameters, such as qe designated from two different models, showed very similar values, which indicates the correctness of the analysis.

Speciation of inorganic arsenic in aqueous samples using a novel hydride generation microfluidic paper-based analytical device (µPAD).

The development of the first microfluidic paper-based analytical device (µPAD) for the speciation of inorganic arsenic in environmental aqueous samples as arsenite (As(III)) and arsenate (As(V)) which implements hydride generation on a paper platform is described. The newly developed µPAD has a 3D configuration and uses Au(III) chloride as the detection reagent. Sodium borohydride is used to generate arsine in the device's sample zone by reducing As(III) in the presence of hydrochloric acid or both As(III) and As(V) (total inorganic As) in the presence of sulfuric acid. Arsine then diffuses across a hydrophobic porous polytetrafluoroethylene membrane into the device's detection zone where it reduces Au(III) to Au nanoparticles. This results in a color change which can be related to the concentration of As(III) or total inorganic As (i.e., As(III) and As(V)) concentration. Under optimal conditions, the µPAD is characterized by a limit of detection of 0.43 mg L-1 for total inorganic As (As(III) + As(V)) and 0.41 mg L-1 for As(III) and a linear calibration range in both cases of 1.2-8.0 mg As L-1. The newly developed µPAD-based method was validated by applying it to groundwater and freshwater samples and comparing the results with those obtained by conventional atomic spectrometric techniques.

Hybrid organic-inorganic membranes based on sulfonated poly (ether ether ketone) matrix and iron-encapsulated carbon nanotubes and their application in CO2 separation.

The need to reduce greenhouse gas emissions dictates the search for new methods and materials. Here, a novel type of inorganic-organic hybrid materials Fe@MWCNT-OH/SPEEK (with a new type of CNT characterized by increased iron content, 5.80 wt%) for CO2 separation is presented. The introduction of nanofillers into a polymer matrix has significantly improved hybrid membrane gas transport (D, P, S, and α CO2/N2 ), and magnetic, thermal, and mechanical parameters. It was found that magnetic casting has improved the alignment and dispersion of Fe@MWCNT-OH carbon nanotubes. At the same time, CNT and polymer chemical modification enhanced interphase compatibility and membrane CO2 separation efficiency. The thermooxidative stability, and mechanical and magnetic parameters of composites were improved by increasing new CNT loading. Cherazi's model turned out to be suitable for describing the CO2 transport through analyzed hybrid membranes. The comparison of the transport and separation properties of the tested membranes with the literature data indicates their potential application in the future and the direction of further research.

Characteristics of Inorganic-Organic Hybrid Membranes Containing Carbon Nanotubes with Increased Iron-Encapsulated Content for CO2 Separation.

Novel inorganic-organic hybrid membranes Fe@MWCNT/PPO or Fe@MWCNT-OH/SPPO (with a new type of CNTs characterized by increased iron content 5.80 wt%) were synthesized for CO2 separation. The introduction of nanofillers into the polymer matrix has significantly improved the hybrid membrane's gas transport (D, P, S, and αCO2/N2), magnetic, thermal, and mechanical parameters. It was found that magnetic casting has improved the alignment and dispersion of Fe@MWCNTs. At the same time, CNTs and polymer chemical modification enhanced interphase compatibility and the membrane's CO2 separation efficiency. The thermo-oxidative stability and mechanical and magnetic parameters of composites were improved by increasing new CNTs loading. Cherazi's model turned out to be suitable for describing the CO2 transport through analyzed hybrid membranes.

On the Potential of a Poly(vinylidenefluoride-co-hexafluoropropylene) Polymer Inclusion Membrane Containing Aliquat® 336 and Dibutyl Phthalate for V(V) Extraction from Sulfate Solutions.

A polymer inclusion membrane (PIM) composed of 50 wt% base polymer poly(vinylidenefluoride-co-hexafluoropropylene), 40 wt% extractant Aliquat® 336, and 10 wt% dibutyl phthalate as plasticizer/modifier provided the efficient extraction of vanadium(V) (initial concentration 50 mg L-1) from 0.1 M sulfate solutions (pH 2.5). The average mass and thickness of the PIMs (diameter 3.5 cm) were 0.057 g and 46 µm, respectively. It was suggested that V(V) was extracted as VO2SO4- via an anion exchange mechanism. The maximum PIM capacity was estimated to be ~56 mg of V(V)/g for the PIM. Quantitative back-extraction was achieved with a 50 mL solution of 6 M H2SO4/1 v/v% of H2O2. It was assumed that the back-extraction process involved the oxidation of VO2+ to VO(O2)+ by H2O2. The newly developed PIM, with the optimized composition mentioned above, exhibited an excellent selectivity for V(V) in the presence of metallic species present in digests of spent alumina hydrodesulfurization catalysts. Co-extraction of Mo(VI) with V(V) was eliminated by its selective extraction at pH 1.1. Characterization of the optimized PIM was performed by contact angle measurements, atomic-force microscopy, energy dispersive X-ray spectroscopy, thermogravimetric analysis/derivatives thermogravimetric analysis and stress-strain measurements. Replacement of dibutyl phthalate with 2-nitrophenyloctyl ether improved the stability of the studied PIMs.

Recent Development of Atmospheric Water Harvesting Materials: A Review.

The lack of freshwater has been threatening many people who are living in Africa, the Middle East, and Oceania, while the discovery of freshwater harvesting technology is considered a promising solution. Recent advances in structured surface materials, metal-organic frameworks, hygroscopic inorganic compounds (and derivative materials), and functional hydrogels have demonstrated their potential as platform technologies for atmospheric water (i.e., supersaturated fog and unsaturated water) harvesting due to their cheap price, zero second energy requirement, high water capture capacity, and easy installation and operation compared with traditional water harvesting methods, such as long-distance water transportation, seawater desalination, and electrical dew collection devices in rural areas or individual-scale emergent usage. In this contribution, we highlight recent developments in functional materials for "passive" atmospheric water harvesting application, focusing on the structure-property relationship (SPR) to illustrate the transport mechanism of water capture and release. We also discuss technical challenges in the practical applications of the water harvesting materials, including low adaptability in a harsh environment, low capacity under low humidity, self-desorption, and insufficient solar-thermal conversion. Finally, we provide insightful perspectives on the design and fabrication of atmospheric water harvesting materials.

Microfluidic Fabrication of Micropolymer Inclusion Beads for the Recovery of Gold from Electronic Scrap.

A composite material, referred to as micropolymer inclusion beads (µPIBs), was fabricated for the first time using a microfluidic technique and applied successfully for the recovery of Au(III) from simulated digests of electronic scrap. Best results for the extraction of Au(III) were achieved with µPIBs consisting of 55% (m/m) poly(vinyl chloride) as the base polymer, 35% (m/m) Aliquat 336 as the extractant, and 10% (m/m) 1-tetradecanol as a modifier. The size and surface morphology of the µPIBs were examined using optical microscopy and scanning electron microscopy, respectively. A batch of 200 mg µPIBs allowed the complete and selective extraction of Au(III) (2.85 mg) from 50 mL of a simulated digest of electronic scrap containing other metal ions, including 1365 mg Cu(II). The extracted Au(III) was quantitatively stripped from the µPIBs into 50 mL of 0.1 mol L-1 solution of thiourea. No Cu(II) and only sub-microgram levels of Cd(II) and Zn(II) were detected in this solution, thus confirming the suitability of the µPIBs for the efficient recovery of Au(III) from digests of electronic scrap. The microfluidic method used in this study is expected to be applicable for the fabrication of µPIBs for the selective separation of other chemical species by varying the composition of the beads.

Limonene Emissions: Do Different Types Have Different Biological Effects?

Limonene is one of the most abundant pollutants indoors, and it contributes to the formation of additional pollutants, such as formaldehyde and photochemical smog. Limonene is commonly used in fragranced consumer products, such as cleaning supplies and air fresheners, which have also been associated with health problems. Limonene can exist in different enantiomeric forms (R-limonene and S-limonene) and be derived from different sources. However, little is known about whether different forms and sources of limonene may have different effects. This research explored whether different types of limonene, at the same concentrations, could elicit different biological effects. To investigate this question, the study employed Aedes aegypti mosquitoes, which have sophisticated olfactory abilities, in olfactometer tests of repellency/attraction. The results indicate that a synthetic source of R-limonene is more repellent than a natural source of R-limonene. In addition, synthetic sources of both R-limonene and S-limonene are not significantly different in repellency. These findings can contribute to our understanding and further exploration of the effects of a common fragrance compound on air quality and health.

Graphene/fluorescein dye-based sensor for detecting As(III) in drinking water.

A complex of reduced graphene oxide (rGO) and fluorescein (FL) dye nanoparticles of size between 50 and 100 nm has been prepared and its sensing performance for detection of As(III) in drinking water has been reported. When As(III) binds to the rGO-FL nanoparticles the relative quenching of fluorescence was increased with increase in As(III) concentration thus provide two linear calibration ranges (0-4.0 mmol L-1 and 4.0-10 mmol L-1). The fluorescence quenching mechanism was investigated by using time-resolved fluorescence spectroscopy and molecular modeling. The detection limit of this sensor has been determined as equal to 0.96 µg L-1 which is about 10 times lower than the WHO stipulated standard for As(III) in drinking water (10 µg L-1). The analytical performance and potential application of the nanosensor was compared to commercial field kits used in arsenic monitoring. The sensor proposed in this study is fast, sensitive and accurate for detection of As(III) in drinking water and environmental samples.

A cross-linked polymer inclusion membrane for enhanced gold recovery from electronic waste.

A cross-linked polymer inclusion membrane (CL-PIM) incorporating the extractant trihexyltetradecylphosphonium bis(2,4,4-trimethylpentyl) phosphinate (Cyphos® IL 104) was developed for the first time for the enhanced Au(III) recovery from aqua regia digests of electronic waste (discarded mobile phones). Cellulose triacetate (CTA), poly(vinyl chloride) (PVC) and poly(vinylidene fluoride-co-hexafluropropylene) (PVDF-HFP) were examined as base polymers. The suitability of poly(ethylene glycol) dimethylacrylate (PEGDMA), poly(ethylene glycol) divinyl ether (PEGDVE) and N-ethylmaleimide (NEM) as cross-linking agents, and the possibility of using triarylsulfonium hexafluorophosphate (TASHFP) and 2,2-dimethoxy-2-phenylacetophenone (DMPA) as initiators were investigated. It was demonstrated that the CL-PIMs composed of Cyphos® IL 104 (30 wt%), PVDF-HFP, PEGDMA (base polymer to cross-linking agent ratio 6:4) and DMPA (1 wt%) or TASHFP (2 wt%) transported Au(III) from 2.5 mol L-1 hydrochloric acid solutions twice as fast as their non-CL-PIM counterpart, showing excellent stability over five successive transport experiments. However, in aqua regia feed solutions (6 mol L-1 acidity) only the CL-PIM containing TASHFP was able to achieve complete Au(III) recovery. AFM studies revealed that the PVDF-HFP-based CL-PIMs had a much higher surface contact area when compared to their non-CL counterpart, and this is proposed to be the reason for their superior transport performance. The CL-PIM that showed good transport efficiency in aqua regia was also applied to aqua regia digests of electronic waste from two mobile phones, and Au(III) was selectively recovered in less than 24 h, while other metals present in significantly higher concentrations were not transported.

Pandemic products and volatile chemical emissions.

The recent pandemic (COVID-19) has seen a sweeping and surging use of products intended to clean and disinfect, such as air sprays, hand sanitizers, and surface cleaners, many of which contain fragrance. However, exposure to fragranced cleaning products has been associated with adverse effects on human health. Products can emit a range of volatile chemicals, including some classified as hazardous, but relatively few ingredients are disclosed to the public. Thus, relatively little is known about the specific emissions from these products. This study investigates the volatile organic compounds (VOCs) emitted from "pandemic products" that are being used frequently and extensively in society. In addition, among these emissions, this study identifies potentially hazardous compounds, compares so-called green and regular versions of products, and examines whether ingredients are disclosed to the public. Using gas chromatography/mass spectrometry, 26 commonly used pandemic products, including 13 regular and 13 so-called green versions, were analyzed for their volatile emissions. Product types included hand sanitizers, air disinfectants, multipurpose cleaners, and handwashing soap. All products were fragranced. The analyses found the products collectively emitted 399 VOCs with 127 VOCs classified as potentially hazardous. All products emitted potentially hazardous compounds. Comparing regular products and green products, no significant difference was found in the emissions of the most prevalent compounds. Further, among the 399 compounds emitted, only 4% of all VOCs and 11% of potentially hazardous VOCs were disclosed on any product label or safety data sheet. This study reveals that pandemic products can generate volatile emissions that could pose risks to health, that could be unrecognized, and that could be reduced, such as by using fragrance-free versions of products.

Use of a Polymer Inclusion Membrane and a Chelating Resin for the Flow-Based Sequential Determination of Copper(II) and Zinc(II) in Natural Waters and Soil Leachates.

A bi-parametric sequential injection method for the determination of copper(II) and zinc(II) when present together in aqueous samples was developed. This was achieved by using a non-specific colorimetric reagent (4-(2-pyridylazo)resorcinol, PAR) together with two ion-exchange polymeric materials to discriminate between the two metal ions. A polymer inclusion membrane (PIM) and a chelating resin (Chelex 100) were the chosen materials to retain zinc(II) and copper(II), respectively. The influence of the flow system parameters, such as composition of the reagent solutions, flow rates and standard/sample volume, on the method sensitivity were studied. The interference of several common metal ions was assessed, and no significant interferences were observed (<10% signal deviation). The limits of detection were 3.1 and 5.6 µg L-1 for copper(II) and zinc(II), respectively; the dynamic working range was from 10 to 40 µg L-1 for both analytes. The newly developed sequential injection analysis (SIA) system was applied to natural waters and soil leachates, and the results were in agreement with those obtained with the reference procedure.

Monitoring of ammonia in marine waters using a passive sampler with biofouling resistance and neural network-based calibration.

A biofouling resistant passive sampler for ammonia, where the semi-permeable barrier is a microporous hydrophobic gas-diffusion membrane, has been developed for the first time and successfully applied to determine the time-weighted average concentration of ammonia in estuarine and coastal waters for 7 days. Strategies to control biofouling of the membrane were investigated by covering it with either a copper mesh or a silver nanoparticle functionalised cotton mesh, with the former approach showing better performance. The effects of temperature, pH and salinity on the accumulation of ammonia in the newly developed passive sampler were studied and the first two parameters were found to influence it significantly. A universal calibration model for the passive sampler was developed using the Group Method Data Handling algorithm based on seawater samples spiked with known concentrations of total ammonia under conditions ranging from 10 to 30 °C, pH 7.8 to 8.2 and salinity 20 to 35. The newly developed passive sampler is affordable, user-friendly, reusable, sensitive, and can be used to detect concentrations lower than the recently proposed guideline value of 160 µg total NH3-N L-1, for a 99% species protection level, with the lowest concentration measured at 17 nM molecular NH3 (i.e., 8 µg total NH3-N L-1 at pH 8.0 and 20 °C). It was deployed at four field sites in the coastal waters of Nerm (Port Phillip Bay), Victoria, Australia. Good agreement was found between molecular ammonia concentrations obtained with passive and discrete grab sampling methods (relative difference, - 12% to - 19%).

Transport of Rhodium(III) from Chloride Media across a Polymer Inclusion Membrane Containing an Ionic Liquid Metal Ion Carrier.

Efficient and selective transport of rhodium(III) across a polymer inclusion membrane (PIM) from a 0.1 mol dm-3 HCl feed solution, also containing iron(III), to a receiving solution containing 0.1 mol dm-3 HCl and 4.9 mol dm-3 NH4Cl was achieved using a phosphonium-type ionic liquid, trioctyl(dodecyl)phosphonium chloride (P88812Cl), as the metal ion carrier. The optimum PIM composition for the Rh(III) transport was 50 wt % poly(vinylidene-co-hexafluoropropylene) (PVDF-HFP), 30 wt % P88812Cl, and 20 wt % plasticizer 2-nitrophenyl octyl ether (2NPOE). The driving force for the Rh(III) transport was suggested to be the concentration difference of the chloride ion between the feed and the receiving solutions. More than 70% rhodium(III) could be recovered from the receiving solution, and no transport of iron(III) was observed; however, the two metal ions cannot be separated by liquid-liquid extraction. This is the first report of selective transport of rhodium(III) across a polymer inclusion membrane.

Exploring the use of Dicranopteris pedata ash as a rare earth fertilizer to Ipomoea aquatica Forsskal.

This study examines a new method to dispose the biomass of a rare earth elements (REE) hyperaccumulator, Dicranopteris pedata, as a REE containing additive of a basal fertilizer for agricultural application. The D. pedata laminas were calcinated to fabricate ashes. The total REE content was 2.65 % for AshDp500, and 4.12 % for AshDp815, respectively. However, as for the heavy metals, Cd or Pb, a higher content could be found in AshDp500 than in AshDp815. The elemental contents of D. pedata ashes are qualified for fertilizer application. Pot experiments were then conducted to investigate the effects of AshDp815 on both the yield and quality of Ipomoea aquatica Forsskal grown in a yellow brown earth, or in a red soil. The application of the ashes increased the I. aquatica height, biomass, vitamin C, soluble protein, and soluble sugar contents, but decreased the I. aquatica nitrate and free amino acids contents. Furthermore, none of the microelements of I. aquatica leaf exceeded the Chinese national standard. The observations indicate the favorable effect of using D. pedata ash on the growth of I. aquatica which is most likely the result from the fertilizer effects of both macroelements and REE present in the ash.