Mid-infrared spectroscopic investigation of the perfect vitrification of poly(ethylene glycol) aqueous solutions.

Crystallization/recrystallization behaviors of poly(ethylene glycol) (PEG) aqueous solutions with water contents (WC's) of ∼36-51 wt % were investigated by temperature-variable mid-infrared spectroscopy. At a WC of 43.2 wt %, crystallization and recrystallization of water and PEG were not observed. At this specific WC value (WCPV), perfect vitrification occurred. Below and above the WCPV value, crystallization/recrystallization behaviors changed drastically. The crystallization temperature below WCPV (237 K) was ∼10 K greater than that above WCPV (226 K). Recrystallization above and below WCPV occurred in one (213 K) and two (198 and 210 K) steps, respectively. These findings resulted from the difference in the (re)crystallization behaviors of water molecules associated with PEG chains with helical and random-coil conformations. These two types of water molecules might have limiting concentrations for their (re)crystallization, indicating that perfect vitrification might have occurred when the concentrations of the two types of water molecules were less than the limiting concentrations of their (re)crystallization.

Separation of inorganic anions on reversed-phase C18 columns with a phosphomolybdate mobile phase.

Reversed-phase high performance liquid chromatography (RP-HPLC) is the most widely used chromatographic method. In addition to hydrophobic interactions, additional interactions such as electrostatic interactions may participate in the retention behaviour of an analyte. This makes it possible to use RP-HPLC for many types of analyte. We describe a simple method for separating inorganic anions on a C18 column, in which retention of inorganic anions is almost entirely due to electrostatic interactions. This leads to rapid separations as well as higher theoretical plate numbers. We used 2 mM phosphoric acid containing a low concentration of disodium molybdate as the mobile phase, which allows UV detection of non-UV-absorbing anions. With this method, we determined eight inorganic anions including several non-UV-absorbing anions photometrically at 220 nm. The detection limits of the examined eight inorganic anions calculated at a signal-to-noise ratio of 3 were between 0.3 and 10 µM. The detector response was linear over three orders of magnitude of inorganic anion concentration. The proposed RP-HPLC/UV method was successfully applied to determine inorganic anions in some water samples.

Automated rapid solid-phase extraction system for separation and preconcentration of trace elements using carboxymethylated polyethyleneimine-type chelating resin.

An automated system for the rapid separation and preconcentration of trace elements was developed. Carboxymethylated polyethyleneimine 600 (CM-PEI600), which is a partially carboxymethylated polyethyleneimine with a molecular weight of 600 Da, was used as a chelating resin to quantitatively recover trace elements under high-flow-rate conditions. For accurately and precisely determining trace elements, even with a rough control of the sample and eluent flow volumes, an internal standardization technique was employed for the solid-phase extraction and separation. A recovery test of the deionized water-based sample solution was conducted using this system, and good results, with a recovery of 92% or higher, were obtained for 11 elements (Cd, Co, Cu, Fe, Mn, Mo, Ni, Pb, Ti, V, and Zn). Eight elements present in certified groundwater and wastewater reference materials (ES-L-1 and EU-L) were separated and preconcentrated using this system. Almost all the determined values were within their tolerance intervals, and no significant differences were observed between the determined and certified values, demonstrating the validity of this method. The time required for the separation and preconcentration using approximately 100 mL of the sample solution was approximately 6.5 min, and theoretically, the system could be used to preconcentrate 17 samples in an hour because extraction and elution could be conducted simultaneously using two cartridges packed with the chelating resin. Using this system equipped with cartridges packed with CM-PEI600 resin, solid-phase extraction and the separation of multiple elements were performed simultaneously, automatically, and rapidly, enabling the accurate and precise determination of trace elements in environmental water and inorganic salts even by rapidly flowing the sample solutions using peristaltic pumps. Compared to NOBIAS Chelate PA-1, a commercially available chelating resin, the CM-PEI600 resin can recover trace elements even under an extremely high flow rate of approximately 50 mL min-1.

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.

Applicability of Internal Standardization with Yttrium to the Solid-phase Extraction of Trace Elements in Groundwater and Wastewater Using an Aminocarboxylic Acid-type Chelating Resin.

Internal standardization was applied to the solid-phase extraction of trace elements using the following commercially available aminocarboxylic acid-type chelating resins: InertSep ME-2, NOBIAS Chelate PA-1, and Presep PolyChelate. The concentration of the trace elements in initial sample solution can be calculated by using the ratio of the added amount of the internal standard element, Y, in the initial sample solution to that in the final solution after the solid-phase extraction, which is proportional to the volume of the sample solution passed through the cartridge, and the ratio of the volume of the initial sample solution to that of a blank solution for preparing the calibration curve. In this solid-phase extraction, strict control of the volumes of the sample solution passed through the cartridge and the final solution after the solid-phase extraction is not needed because these are not used in the calculation of the trace element concentration. The solid-phase extraction with the internal standardization using Y could be applied to the separation and preconcentration of some trace elements, namely Cd, Co, Cu, Fe, Ni, Pb, Ti, and Zn in an artificial seawater spiked with the elements and some certified reference materials, EnviroMAT ES-L-1 Ground Water and EU-L-3 Waste Water, without any interference.

Potential of Carboxymethylated Polyallylamine as a Functional Group on Chelating Resin for Solid-Phase Extraction of Trace Elements.

New chelating resins immobilizing carboxymethylated polyallylamine (CM-PAA) were prepared by immobilizing PAAs with some molecular weights on methacrylate resins and then carboxymethylating a part of amino groups in the PAAs using various amounts of sodium monochloroacetate. The molecular weight of PAA barely affected both the amount of PAA immobilized on the resin and the relationship between the carboxymethylation (CM) rate and the ratio of the amount of monochloroacetate used in the CM step. The selectivity of CM-PAA resin for solid-phase extraction of trace elements was almost the same as that of a resin immobilizing carboxylymethylated polyethyleneimine; 10 elements, namely Cd, Co, Cu, Fe, Mo, Ni, Pb, Ti, V, and Zn, could be quantitatively recovered over a wide pH range and alkali and alkaline earth elements were scarcely extracted under acidic and neutral conditions. The CM-PAA resin was applicable to the separation and preconcentration of the elements in a certified reference material (Waste Water, EU-L-1) and a real environmental water sample (ground water).

Size resolved characteristics of urban and suburban bacterial bioaerosols in Japan as assessed by 16S rRNA amplicon sequencing.

To study the size-resolved characteristics of airborne bacterial community composition, diversity, and abundance, outdoor aerosol samples were analysed by 16S rRNA gene-targeted quantitative PCR and amplicon sequencing with Illumina MiSeq. The samples were collected using size-resolved samplers between August and October 2016, at a suburban site in Toyama City and an urban site in Yokohama City, Japan. The bacterial communities were found to be dominated by Actinobacteria, Firmicutes, and Proteobacteria. At the genus level, we found a high abundance of human skin-associated bacteria, such as Propionibacterium, Staphylococcus, and Corynebacterium, in the urban site. Whereas, a high abundance of bacteria associated with soil and plants, such as Methylobacterium and Sphingomonas, was observed in the suburban site. Furthermore, our data revealed a shift in the bacterial community structure, diversity, and abundance of total bacteria at a threshold of 1.1-µm diameter. Interestingly, we observed that Legionella spp., the causal agents of legionellosis in humans, were mainly detected in > 2.1 µm coarse particles. Our data indicate that local environmental factors including built environments could influence the outdoor airborne bacterial community at each site. These results provide a basis for understanding the size-resolved properties of bacterial community composition, diversity, and abundance in outdoor aerosol samples and their potential influence on human health.

Adsorption and aggregation of Fe(III)-hydroxy complexes during the photodegradation of phenol using the iron-added-TiO(2) combined system.

The behavior of Fe(III) aquacomplexes in TiO(2) suspensions in the degradation of phenol has been investigated. The most active Fe(OH)(2+) species adsorbed on the surface of TiO(2) retards the conversion of Fe(OH)(2+) into oligomers and therefore increases the percentage of Fe(OH)(2+) with irradiation time, with a consequent enhancement in the catalytic cycle of Fe(III)/Fe(II) and excited charge traps by Fe(III) in the iron-TiO(2) system. The influence of iron addition on TiO(2) was obtained when the regeneration of [Fe(OH)(2+)] remained continuous with irradiation time. In an optimum TiO(2) suspension (0.5g/L) with the addition of 0.1mM Fe(III), the measured k(obs) values for phenol degradation were enhanced for the higher adsorption of Fe(OH)(2+) on the reactive surface of TiO(2) at a specified irradiation time.

Phosphomethylated Polyethyleneimine-immobilized Chelating Resin: Role of Phosphomethylation Rate on Solid-Phase Extraction of Trace Elements.

Chelating resins immobilizing phosphomethylated polyethyleneimine (PM-PEI) with different phosphomethylation (PM) rates were prepared by using different amounts of both phosphonic acid and paraformaldehyde in the phosphomethylation of PEI immobilized on a methacrylate resin as a base resin. The extraction of many elements improved with increasing PM rate; REEs, Be, Fe, Mo, Ti, and V were quantitatively extracted at pH 2. The elution of the elements tended to become difficult with increasing PM rate. When a PM-PEI resin with a PM rate of 0.26 was used, REEs and Be could be eluted using 0.2 mol L-1 EDTA solution adjusted to a pH of 7 and 3 mol L-1 nitric acid, respectively, although the elution of Fe, Mo, Ti, and V was insufficient. The PM-PEI resin could be reused at least 10 times to recover REEs and Be without the influence of any other elements. The PM-PEI resin could be applied to a recovery test using artificial seawater spiked with REEs, except for Sc, Tm, Yb, and Lu, and the separation of the REEs in NIST SRM 1515 Apple Leaves.

Thermal Decomposition Behavior of a Chelating Resin Immobilizing Carboxymethylated Polyethyleneimine: Possibility of Estimation of Carboxymethylation Rate.

Chelating resins immobilizing carboxymethylated polyethyleneimine (CM-PEI) with different carboxymethylation rates were prepared. The thermal decomposition behavior of CM-PEI resins was investigated using thermogravimetry-differential thermal analysis/photo ionization-quadrupole mass spectrometry (TG-DTA/PI-QMS) and ion attachment ionization-quadrupole mass spectrometry equipped with direct inlet probe (DIP/IA-QMS). The obtained results suggested that the carboxymethyl group decomposed at relatively low temperature (150 °C - 300 °C); the peak areas at m/z 45 and 59 in TG-DTA/PI-QMS and m/z 58, 70, and 72 in DIP/IA-QMS significantly increased with increasing carboxymethylation rate. These relationships should be useful for estimating the carboxymethylation rate of CM-PEI resin.

A porous sintered material consisting of Presep PolyChelate as a chelating resin and particulate polyethylene as a thermoplastic binder for solid-phase extraction of trace elements.

Cylinder-type and disk-type sintered materials consisting of Presep PolyChelate, which is a commercially available chelating resin immobilizing carboxymethylated polyethyleneimine as a functional group, and particulate polyethylene as a thermoplastic binder were prepared using a polymer sintering technique. The sintered materials had a continuously porous structure. The sintering process at 130 °C for 20 min did not affect the ability of the chelating resin in the sintered materials; the selectivity of the sintered material was almost the same as that of the particulate chelating resin which was not sintered. The sintering materials could quantitatively extract 11 kinds of trace elements, namely Cd, Co, Cu, Fe, Mn, Mo, Ni, Pb, Ti, V, and Zn, at pH 5.5. When the disk-type sintered material was used, the recoveries of these elements remained almost constant at a flow rate of at least 50 mL min-1; the extracted elements could be eluted using 10 mL of 3 mol L-1 nitric acid at a flow rate of 5 mL min-1. Solid-phase extraction using the disk-type sintered material was applied to the separation and preconcentration of trace elements prior to their inductively coupled plasma atomic emission spectrometric determination. The method was applicable to analyses of certified reference materials (EnviroMAT ES-L-1 ground water and EU-L-3 waste water) and a commercially available table salt.

Rapid coprecipitation technique using yttrium hydroxide for the preconcentration and separation of trace elements in saline water prior to their ICP-AES determination.

Yttrium hydroxide quantitatively coprecipitated Be(II), Ti(IV), Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), Cd(II), and Pb(II) at pH 9.6 - 10.0 for seawater and pH 10.5 - 11.4 for a table-salt solution. The coprecipitated elements could be determined by inductively coupled plasma atomic emission spectrometry; yttrium was used as an internal standard element. The detection limits ranged from 0.001(6) microg (Mn(II)) to 0.22 microg (Zn(II)) in 100 mL of sample solutions. The operation time required to separate 11 elements was approximately 30 min.

Improvement of Chromium(VI) Extraction from Acidic Solutions Using a Poly(vinyl chloride)-based Polymer Inclusion Membrane with Aliquat 336 as the Carrier.

An important reason for the inefficient extraction of Cr(VI) from its acidic solutions into polymer inclusion membranes (PIMs), consisting of poly(vinyl chloride) as the base-polymer and Aliquat 336 as the carrier, was found to be associated with the leaching of Aliquat 336 from the PIMs into the solutions, where it subsequently reduced the anionic Cr(VI) species to cationic Cr(III) species. The PIM extraction efficiency for Cr(VI) was significantly improved by the addition of NaNO3 to the solutions, which suppressed the leaching of Aliquat 336 and the reduction of Cr(VI) to Cr(III).

Diffusion-Controlled Recrystallization of Water Sorbed into Poly(meth)acrylates Revealed by Variable-Temperature Mid-Infrared Spectroscopy and Molecular Dynamics Simulation.

Recrystallization behaviors of water sorbed into four poly(meth)acrylates, poly(2-methoxyethyl acrylate), poly(tetrahydrofurfuryl acrylate), poly(methyl acrylate), and poly(methyl methacrylate), are investigated by variable-temperature mid-infrared (VT-MIR) spectroscopy and molecular dynamics (MD) simulation. VT-MIR spectra demonstrate that recrystallization temperatures of water sorbed into the polymers are positively correlated with their glass-transition temperatures reported previously. The present MD simulation shows that a lower-limit temperature of the diffusion for the sorbed water and the glass-transition temperatures of the polymers also have a positive correlation, indicating that the recrystallization is controlled by diffusion mechanism rather than reorientation mechanism. Detailed molecular processes of not only recrystallization during rewarming but also crystallization during cooling and hydrogen-bonding states of water in the polymers are systematically analyzed and discussed.

Combined biological and photocatalytic treatment for the mineralization of phenol in water.

Phenol is degraded by biological treatment, however mineralization requires long time. To decrease the time and operational cost necessary for the mineralization of phenol, an optimum operation condition of the combined biological-photocatalytical treatment was investigated. The mineralization of phenol (50 mg l(-1)) was conducted in a flow-type biomembrane tank combined with a batch-type TiO2-suspended photocatalytic reactor. Phenol was degraded biologically to the concentration of 6.8 mg l(-1), an effective concentration for further photocatalytic treatment. After the biological treatment, the biotreated phenol was treated photocatalytically to complete the mineralization of phenol. The combined treatment shortened the mineralization time compared to the biological treatment and electric cost compared to the photocatalytic treatment only. The combined treatment may be suitable for a short-time mineralization of phenol in wastewater.

Photocatalytic degradation of phenol by visible light-responsive iron-doped TiO2 and spontaneous sedimentation of the TiO2 particles.

Fe-doped TiO2 was prepared by the calcination of Fe(x)TiS(2) (x=0, 0.002, 0.005, 0.008, 0.01) and characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and UV-visible diffuse reflectance spectra. All the Fe-doped TiO2 were composed of an anatase crystal form and showed red shifts to a longer wavelength. The activity of the Fe-doped TiO2 for the degradation of phenol was investigated by varying the iron content during UV (365nm) and visible light (405nm and 436nm) irradiation. The degradation rate depended on the Fe content and the Fe-doped TiO2 was responsive to the visible light as well as the elevated activity toward UV light. The molar ratio of 0.005 was the optimum for both the UV and visible light irradiations. The result was discussed on the basis of the balance of the excited electron-hole trap by the doped Fe(3+) and their charge recombination on the doped Fe(3+) level. The Fe-doped TiO2 (x=0.005) was more active than P25 TiO2 under solar light irradiation. The suspended Fe-doped TiO2 spontaneously precipitated once the stirring of the reaction mixture was terminated.

Chelating resin immobilizing carboxymethylated polyethyleneimine for selective solid-phase extraction of trace elements: Effect of the molecular weight of polyethyleneimine and its carboxymethylation rate.

The effect of the molecular weight of polyethyleneimine (PEI), defined as a compound having two or more ethyleneamine units, and of its carboxymethylation rate (CM/N), represented by the ratio of ion-exchange capacity to the amount of N on the resin, on the selective solid-phase extraction ability of the chelating resin immobilizing carboxymethylated (CM) PEI was investigated. The chelating resins (24 types) were prepared by immobilization of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, PEI300 (MW=ca. 300), and PEI600 (MW=ca. 600) on methacrylate resins, followed by carboxymethylation with various amounts of sodium monochloroacetate. When resins with approximately the same CM/N ratio (0.242-0.271) were used, the recovery of Cd, Co, Cu, Fe, Ni, Pb, Ti, Zn, and alkaline earth elements increased with increasing the molecular weight of PEIs under acidic and weakly acidic conditions; however, the extraction behavior of Mo and V was only slightly affected. This was probably due to the increase in N content of the resin, resulting in an increase in carboxylic acid groups; the difference in the molecular weight of PEIs immobilized on the resin exerts an insignificant influence on the selective extraction ability. The CM/N ratio considerably affected the extraction behavior for various elements. Under acidic and neutral conditions, the recovery of Cd, Co, Cu, Fe, Ni, Pb, Ti, and Zn increased with increasing CM/N values. However, under these conditions, the recovery of alkaline earth elements was considerably low when a resin with low CM/N ratio was used. This is presumably attributed to the different stability constants of the complexes of these elements with aminocarboxylic acids and amines, and to the electrostatic repulsion between the elements and the protonated amino groups in the CM-PEI. The recovery of Mo and V decreased or varied with increasing CM/N values, suggesting that the extraction of these elements occurred mainly by the anion-exchange reaction. For the separation and preconcentration of trace elements in samples containing large amounts of alkali and alkaline earth elements, the CM-PEI600 resin with CM/N=0.131 (Cu(II) extraction capacity, 0.37mmol g(-)(1)) was found to be the most suitable because it scarcely extracts alkali and alkaline earth elements under acidic and neutral conditions. This resin proved to be convenient for separating and preconcentrating Cd, Co, Cu, Fe, Mn, Mo, Ni, Pb, V, and Zn in the certified reference materials (EnviroMAT EU-L-1 wastewater and ES-L-1 ground water) and commercially available table salt.

Determination of cadmium in river water by electrothermal atomic absorption spectrometry after internal standardization-assisted rapid coprecipitation with lanthanum phosphate.

Cadmium ranging from 1 - 8 ng could be coprecipitated quantitatively with lanthanum phosphate at pH 5 - 6 from up to 200 mL of river water samples spiked with 5 microg of indium as an internal standard. Cadmium and indium coprecipitated were measured by using electrothermal atomic absorption spectrometry. The cadmium content in the original sample solution could be determined by internal standardization with indium. Since complete collection of the precipitate and strict adjustment of the volume of the final solution after coprecipitation are not required in this method, the precipitate could be collected by using decantation and centrifugation, and then dissolved with 1 mL of about 2.4 mol L(-1) nitric acid. The proposed method is simple and rapid, and enrichment close to 200-times can be attained; the detection limit (3sigma, n = 6) was 0.63 ng L(-1) in 200 mL of the sample solution.

Application of internal standardization to rapid coprecipitation technique using lanthanum phosphate for flame atomic absorption spectrometric determination of iron and lead.

By applying an internal standardization, we could use a rapid coprecipitation technique using lanthanum phosphate as a coprecipitant for preconcentration of iron(III) and lead in their flame atomic absorption spectrometric determination. Indium as an internal standard was added to the initial sample solution together with lanthanum and phosphoric acid; the coprecipitation of iron(III) and lead was then carried out at pH about 3. After measuring the atomic absorbances of iron, lead, and indium in the final sample solution, we determined the contents of iron(III) and lead in the original sample solution by using the internal standardization with indium. In this method, complete collection of the precipitate was not required after the coprecipitation of iron(III), lead, and indium, because the ratio of the recovery of iron(III) or lead to that of indium was almost constant regardless of the recovery of the precipitate. This method was simple and rapid, and was available for the determination of 2-300 micrograms L-1 of iron(III) and 5-400 micrograms L-1 of lead in some water samples.

Chelating materials immobilizing carboxymethylated pentaethylenehexamine and polyethyleneimine as ligands.

This article presents an overview of our recent progress on the development of chelating materials. Carboxymethylated pentaethylenehexamine (CM-PEHA) and polyethyleneimine (CM-PEI) as chelating ligands show excellent performance for the solid-phase extraction of trace elements. Chelating resins immobilizing these ligands can be readily prepared by immobilizing PEHA and PEI on methacrylate resins and then carboxymethylating them. Chelating fiber can also be prepared with a wet spinning technique using a mixture of a viscose solution and a solution containing fine particulate CM-PEHA resin or CM-PEI. The potentials of these chelating materials for the separation and preconcentration of trace elements are outlined.