Synthesis of recyclable and light-weight graphene oxide/chitosan/genipin sponges for the adsorption of diclofenac, triclosan, and microplastics.

Emerging micropollutants, such as pharmaceuticals and microplastics (MPs), have become a pressing water environmental concern. The aim of this study is to synthesize chitosan sponges using graphene oxide (GO) and genipin (GP) for the removal of pharmaceuticals (diclofenac (DCF) and triclosan (TCS)) and MPs, verify their adsorption mechanisms, evaluate the effects of temperature, pH, and salinity on their adsorption capacities, and determine their reusability. The GO5/CS/GP sponge exhibited a macroporous nature (porosity = 95%, density = 32.6 mg/cm3). GO and cross-linker GP enhanced the adsorption of DCF, TCS, and polystyrene (PS) MPs onto the CS sponges. The adsorption of DCF, TCS, and PS MPs involved multiple steps: surface diffusion and pore diffusion of the sponge. The adsorption isotherms demonstrated that Langmuir model was the most fitted well model to explain adsorption of TCS (qm = 7.08 mg/g) and PS MPs (qm = 7.42 mg/g) on GO5/CS/GP sponge, while Freundlich model suited for DCF adsorption (qm = 48.58 mg/g). DCF adsorption was thermodynamically spontaneous and endothermic; however, the adsorption of TCS and PS MPs was exothermic (283-313 K). The optimal pH was 5.5-7 due to the surface charge of the GO5/CS/GP sponge (pHzpc = 5.76) and ionization of DCF, TCS, and PS MPs. As the salinity increased, DCF removal efficiency drastically decreased due to the weakening of electrostatic interactions; however, TCS removal efficiency remained stable because TCS adsorption was mainly caused by hydrophobic and π-π interactions rather than electrostatic interaction. The removal of PS MPs was enhanced by the electrostatic screening effects of high Na+ ions. PS nanoplastics (average size = 26 nm) were removed by the GO5/CS/GP sponge at a rate of 73.0%, which was better than that of PS MPs (41.5%). In addition, the GO5/CS/GP sponge could be recycled over five adsorption-desorption cycles.

Visible-light-induced self-propelled nanobots against nanoplastics.

The accumulation of plastic debris in aquatic organisms has raised serious concerns about the potential health implications of their incorporation into the food chain. However, conventional water remediation techniques are incapable of effectively removing nanoplastics (NPs) smaller than 200 nm, which can have harmful effect on animal and human health. Herein, we demonstrate the "on-the-fly" capture of NPs through their enlargement (approximately 4,100 times) using self-propelled nanobots composed of a metal-organic framework. Under visible-light irradiation, the iron hexacyanoferrate (FeHCF) nanobot exhibits fuel-free motion by electrostatically adsorbing NPs. This strategy can contribute to reducing plastic pollution in the environment, which is a significant environmental challenge. Light-induced intervalence charge transfer in the FeHCF nanobot lattice induces bipolarity on the nanobot surface, leading to the binding of negatively charged NPs. The local electron density in the lattice then triggers self-propulsion, thereby inducing agglomeration of FeHCF@NP complexes to stabilize their metastable state. The FeHCF nanobot exhibits a maximum removal capacity of 3,060 mg∙g-1 and rate constant of 0.69 min-1, which are higher than those recorded for materials reported in the literature.

Ex situ soil washing of highly contaminated silt loam soil using core-crosslinked amphiphilic polymer nanoparticles.

Non-ionic surfactants (Triton X-100 and Brij 30) and core-crosslinked amphiphilic polymer (CCAP) nanoparticles were used as extractants in the ex situ soil washing of silt loam soil contaminated with large quantities of petroleum oil, and their soil-washing performances were compared. Following washing with the surfactants, highly turbid aqueous solutions containing large numbers of soil and petroleum oil particles were produced. In contrast, the CCAP nanoparticles successfully extracted the petroleum oils from the soil samples without the formation of such a turbid aqueous solution. In addition, the CCAP nanoparticles extracted 96% of the petroleum oils, which is a significantly larger quantity than that by Brij 30 and Triton X-100 under equivalent conditions. Indeed, owing to their crosslinked micelle-like structure, the CCAP nanoparticles maintained their nanostructure even upon contact with a highly contaminated silt loam soil matrix, thereby resulting in the extraction of only the hydrophobic oily contaminants from the soil matrix and avoiding the formation of dispersions of soil particles and hydrophobic contaminants. As such, CCAP nanoparticles could be considered as suitable washing materials for highly contaminated silt loam soils.

Remediation of metal-contaminated marine sediments using active capping with limestone, steel slag, and activated carbon: a laboratory experiment.

The objectives of this study are to assess the effectiveness of limestone (LS), steel slag (SS), and activated carbon (AC) as capping materials to sequester trace metals including As, Cd, Cr, Cu, Ni, Pb, and Zn in heavily contaminated marine sediments and to minimize the release of these metals into the water column. A flat flow tank was filled with 10 mm of capping material, contaminated sediments, and seawater, and the metal concentrations were monitored over 32 d. After completion of the flow tank experiments, the sediments below the capping material were sampled and were sequentially extracted. SS effectively reduced the As, Cr, Cu, Ni, Pb, and particularly Cd elution from the contaminated sediments to the overlying seawater. Adsorption and surface precipitation were the key mechanisms for interrupting the release of cationic trace metals by SS. LS was appropriate for interrupting the release of only Cu and Pb with high hydrolysis reaction constants. AC capping could interrupt the release of Cr, Cu, Ni, and particularly Zn from the sediments by binding with the metals via electrostatic interaction. The results obtained from the sequential extraction revealed that LS capping is appropriate for stabilizing Zn, whereas AC is appropriate for Cd and Pb. LS, SS, and AC can be applied effectively for remediation of sediments contaminated by trace metals because it interrupts their release and stabilizes the trace metals in the sediments.

Employment status and unmet dental care needs in South Korea: a population-based panel study.

OBJECTIVES: This study was designed to evaluate whether employment status is associated with the experience of unmet dental care needs. METHODS: A total of 4620 workers were retrieved from Korea Health Panel data (2010-2013), and potential relationships were explored among their income levels, changes in employment and unmet dental care needs. RESULTS: Among the 4620 workers, 17.3% said they had failed at least once to get dental treatment or check-up, despite their needs. Precarious workers and those not in employment were more likely to experience unmet dental care needs due to economic burden compared with permanent workers (OR 1.36, 1.40, respectively). In addition, people in low-income group were 4.46 times more likely to experience unmet dental care needs caused by economic burden, compared with those with the highest income. CONCLUSION: This disparity means that precarious workers and those not in employment are more likely to face barriers in obtaining needed health services. Given the insecure employment status of low income people, meeting their healthcare needs is an important consideration.

Quaternized Amphiphilic Block Copolymers/Graphene Oxide and a Poly(vinyl alcohol) Coating Layer on Graphene Oxide/Poly(vinylidene fluoride) Electrospun Nanofibers for Superhydrophilic and Antibacterial Properties.

Poly(vinylidene fluoride) (PVDF) is common polymer for electrospinning, however, its high hydrophobicity is a major drawback, which cause fouling. To introduce hydrophilicity and antibacterial activity, quaternary ammonium-functionalized amphiphilic diblock copolymers were synthesized and blended with a PVDF/graphene oxide (GO) solution, then, electrospun and coated with a hydrophilic polymer, poly(vinyl alcohol) (PVA). The amphiphilic block copolymer, consisting of a hydrophobic poly(methyl methacrylate) block and a hydrophilic poly[N,N-2-(dimethylamino)-ethyl methacrylate) block (PMMA-b-PDMAEMA), was synthesized. Polymeric quaternary ammonium with three different alkyl chain lengths (C2, C4, and C8) were successfully introduced to obtain as q-PMMA-b-PDMAEMA. The q-PMMA-b-PDMAEMA in the nanofiber matrix was confirmed by C=O bands (1734 cm-1) in the Fourier transform infrared spectra. Nano-sized spherical protuberances were distributed on the surface as revealed by field emission scanning and transmission electron microscopies. The PVDF/GO/q-PMMA-b-PDMAEMA@PVA nanofibers has superhydrophilic properties (water contact angle = 0-20°) and the pure water flux was generally improved by increasing the alkyl chain length. When introducing the longest alkyl chain (C8,OBC), the total fouling ratio was the lowest (49.99%) and the bacteria removal capacities after 60 min were the highest for both Escherichia coli (4.2 × 105 CFU/mg) and Staphylococcus aureus (6.1 × 105 CFU/mg) via growth inhibition and cytoplasmic membrane damage.

Blend-electrospun graphene oxide/Poly(vinylidene fluoride) nanofibrous membranes with high flux, tetracycline removal and anti-fouling properties.

Graphene oxide (GO)/poly(vinylidene fluoride) (PVDF) electrospun nanofibrous membranes (ENMs) have been fabricated to remove tetracycline (TC) from water via adsorptive-filtration. The pure water permeation flux of GO/PVDF ENMs (27,407-29,337 LMH/bar) was increased compared with that of PVDF ENMs. The flow pore diameter was steadily reduced by increasing the GO content from 0 to 1.5 wt% in the GO/PVDF ENMs. The maximum TC adsorption capacity of GO is 720.26 mg/g (Langmuir model) and GO retained its TC adsorption property after incorporation into GO/PVDF ENMs during water filtration (transmembrane pressure = 0.91 bar). The maximum experimental TC removal capacity (qa,exp) was 17.92 mg/g with 1.5 wt% of GO (GO1.5/PVDF) ENMs, which was similar to the modified dose-response model value of 18.03 mg/g. In the presence of natural organic matter, TC adsorption was enhanced, because hydrophobic organic carbon improved hydrophobic and π-π interactions. The presence of Cu(II) further improved the TC adsorption capacity of GO1.5/PVDF ENMs through cation bridging. However, the presence of Ca(II) hindered TC adsorption by an electron shielding effect. For examining anti-fouling activity of GO1.5/PVDF ENMs, the log removal values of both bacteria, Escherichia coli and Staphylococcus aureus, were maintained at over 5 during water filtration. In addition, incorporation of GO in PVDF ENMs prevents bovine serum albumin (BSA) adsorption by both increasing the hydrophilicity of the ENMs forming hydration layer on the surface and electrostatic repulsion between both negatively charged BSA and GO in GO1.5/PVDF ENMs (zeta potential = - 14.14 mV, deionized water at pH 6).

Strong chromate-adsorbent based on pyrrolic nitrogen structure: An experimental and theoretical study on the adsorption mechanism.

Chromate is considered a toxic contaminant in various water sources because it poses a risk to animal and human health. To meet the stringent limits for chromium in water and wastewater, pyrrolic nitrogen structure was investigated as a chromate adsorbent for aqueous solutions, employing a polypyrrole coating on carbon black. The characteristics of the adsorbent were analyzed by high-resolution transmission electron microscopy, energy-filtered transmission electron microscopy, and X-ray photoelectron spectroscopy. Chromate was adsorbed as both Cr(III) and Cr(VI). The chromate adsorption capacity increased (from 50.84 to 174.81 mg/g) with increasing amounts of pyrrole monomers (from 50 to 86%) in the adsorbent. The adsorption capacity was well-correlated with the pyrrolic nitrogen content (from 2.06 to 6.57 at%) in the adsorbent, rather than other types of nitrogen. The optimized adsorption capacity (174.81 mg/g in the equilibrium batch experiment and 211.10 mg/g at an initial pH of 3) was far superior to those of conventional adsorbents. We investigated the mechanism behind this powerful chromate adsorption on pyrrolic nitrogen via physical/chemical analyses of the pH-dependent adsorption behavior, supported by first-principles calculation based on density functional theory. We found that Cr(III) and Cr(VI) adsorption followed different reaction paths. Cr(III) adsorption occurred in two sequential steps: 1) A Jones oxidation reaction (JOR)-like reaction of Cr(VI) with pyrrolic N that generates Cr(III), and 2) Cr(III) adsorption on the deprotonated pyrrolic N through Cr(III)-N covalent bonding. Cr(VI) adsorption followed an alternative path: hydrogen-bonding to the deprotonation-free pyrrolic N sites. The pH-dependent fractional deprotonation of the pyrrolic N sites by the JOR-like reaction in the presence of chromate played an important role in the adsorption.

Use of hybrid composite particles prepared using alkoxysilane-functionalized amphiphilic polymer precursors for simultaneous removal of various pollutants from water.

In this study, we present new inorganic-organic hybrid particles and their possible application as an adsorbent for simultaneous removal of hydrophobic and hydrophilic pollutants from water. These hybrid particles were prepared using tailor-made alkoxysilane-functionalized amphiphilic polymer precursors (M-APAS), which have amphiphilic polymers and reactive alkoxysilane groups attached to the same backbone. Through a single conventional sol-gel process, the polymerization of M-APAS and the chemical conjugation of M-APAS onto silica nanoparticles was simultaneous, resulting in the formation of hybrid particles (M-APAS-SiO2) comprised of hyperbranch-like amphiphilic polymers bonded onto silica nanoparticles with a relatively high grafting efficiency. A test for the adsorption of water-soluble dye (organe-16) and water insoluble dye (solvent blue-35) onto the hybrid particles was performed to evaluate the possibility of adsorbing hydrophilic and hydrophobic compound within the same particle. The hybrid particle was also evaluated as an adsorbent for the removal of contaminated water containing various pollutants by wastewater treatment test. The hybrid particle could remove phenolic compounds from wastewater and the azo dye reactive orange-16 from aqueous solutions, and it was easily separated from the treated wastewater because of the different densities involved. These results demonstrate that the hybrid particles are a promising sorbent for hydrophilic and/or hydrophobic pollutants in water.

Lead and copper removal from aqueous solutions using carbon foam derived from phenol resin.

Phenolic resin-based carbon foam was prepared as an adsorbent for removing heavy metals from aqueous solutions. The surface of the produced carbon foam had a well-developed open cell structure and the specific surface area according to the BET model was 458.59m(2)g(-1). Batch experiments showed that removal ratio increased in the order of copper (19.83%), zinc (34.35%), cadmium (59.82%), and lead (73.99%) in mixed solutions with the same initial concentration (50mgL(-1)). The results indicated that the Sips isotherm model was the most suitable for describing the experimental data of lead and copper. The maximum adsorption capacity of lead and copper determined to Sips model were 491mgg(-1) and 247mgg(-1). The obtained pore diffusion coefficients for lead and copper were found to be 1.02×10(-6) and 2.42×10(-7)m(2)s(-1), respectively. Post-sorption characteristics indicated that surface precipitation was the primary mechanism of lead and copper removal by the carbon foam, while the functional groups on the surface of the foam did not affect metal adsorption.

Enhanced phosphate selectivity from wastewater using copper-loaded chelating resin functionalized with polyethylenimine.

In water and wastewater, phosphate is considered a critical contaminant due to cause algae blooms and eutrophication. To meet the stringent regulation of phosphate in water, a new commercial chelating resin functionalized with polyethylenimine was tested for phosphate removal by loading Cu(2+) and Fe(2+)/Fe(3+) to enhance selectivity for phosphate. Batch and column experiments showed that CR20-Cu exhibited high selectivity for phosphate over other strong anions such as sulfate. The average binary phosphate/nitrate and phosphate/sulfate factors for CR20-Cu were calculated to be 7.3 and 4.8, respectively, which were more than 0.97 and 0.22 for a commercial anion exchanger (AMP16). The optimal pH for the phosphate removal efficiency was determined to be 7. According to the fixed-bed column test, the breakthrough sequence for multiple ions was HPO4(2-)>SO4(2-)>NO3(-)>Cl(-). Saturated CR20-Cu can be regenerated using 4% NaCl at pH 7. More than 95% of the phosphate from CR20-Cu was recovered, and the phosphate uptake capacity for CR20-Cu was not reduced after 7 regeneration cycles.