Cross-sectional microstructural analysis to evaluate the crack growth pattern of weathered marine plastics.

Fragmentation of degraded plastics and release of smaller secondary microplastics is usually attributed to the growth of environmental stress cracks. Analysis of crack patterns derived from chemical degradation can be useful not only for assessing the cause of plastic fracture and evaluating the useful lifetime of a product, but it can also potentially provide valuable information on the generation of microplastics. However, the literature with respect to microplastics generation is generally limited to surface observations of polypropylene and polyethylene. Here, we used ion-beam milling to prepare cross-sections of fragments of 15 plastic products made from five commodity plastics (polypropylene, polyethylene, polystyrene, polyvinyl chloride, and polyethylene terephthalate) that were collected at two beaches in Japan, and then we examined the microstructures of those cross-sections by means of scanning electron microscopy and energy dispersive X-ray spectroscopy. Crack growth in the depth direction was examined to provide insights into microplastic generation behavior. In all of the polypropylene samples, and some of the low-density polyethylene and polystyrene samples, cracks with a depth exceeding 100 µm from the sample surface were observed. Considering that crack growth causes fracture of degraded plastic and microplastic release, these observations suggest the release of sharp-edged microplastics from the crack fracture surface. In contrast, in the high-density polyethylene and polyvinyl chloride samples, crack growth was limited to within 20 µm of the sample surface, suggesting the release of irregularly shaped microplastics and additive particles. The present results suggest that the degradation behavior of plastic products in the depth direction is dependent on the type of plastic.

Identification and quantification of additive-derived chemicals in beached micro-mesoplastics and macroplastics.

Although marine plastic debris are expected to retain various chemical additives, little is known about the additives that are retained. We conducted a screening analysis of additives in 261 macroplastic and micro-mesoplastic debris from two beaches. We detected 52 chemicals-antioxidants, phthalates, ultraviolet stabilizers, hindered amine light stabilizers, and flame retardants-and quantified the concentrations of 15 of them. Comparison of the concentrations of Irgafos 168, an antioxidant stabilizer, among sample categories indicated that leaching had occurred from micro-mesoplastics. Differences in diffusion rates between polymer types may explain faster leaching from polyethylene than polypropylene. The significant amounts of Irgafos 168 retained in even micro-mesoplastics indicated the importance of plastics as a vector of additives. This study provides fundamental data needed to assess the risks to organisms from exposure to plastic additives and to understand the effect of stabilizers on the aging behavior of marine plastics.

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).

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.

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.

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.

Potential of Presep(®) PolyChelate as a chelating resin: comparative study with some aminocarboxylic acid-type resins.

The potential of Presep(®) PolyChelate as a chelating resin was studied in detail. The chelating resin with extraction capacity for Cu of 0.30 mmol L(-1) could quantitatively extract Cd, Co, Cu, Fe, Mo, Ni, Pb, V, and Zn at pH 4 or 5.5; however, only very scant amounts of Na, K, Mg, and Ca were captured at pH levels below 7. The quantitative extraction could be achieved in 100 - 1000 mL of artificial seawater and at a flow rate of 3 - 30 mL min(-1). The performance of Presep(®) PolyChelate was compared to the other aminocarboxylic acid-type chelating resins, including Nobias Chelate-PA1, Chelex 100, Muromac B-1, Lewatit TP 207, and NTA Superflow, under the same conditions. The solid-phase extraction of the nine elements in the certified reference material (ES-L-1, ground water) and a commercially available table salt was also demonstrated.

Chelating fibers prepared with a wet spinning technique using a mixture of a viscose solution and a polymer ligand for the separation of metal ions in an aqueous solution.

Chelating fibers containing polymer ligands such as carboxymethylated polyallylamine, carboxymethylated polyethyleneimine, and a copolymer of diallylamine hydrochloride/maleic acid were prepared with a wet spinning technique using mixtures of a viscose solution and the polymer ligands. The chelating fibers obtained effectively adsorbed various metal ions, including Cd(II), Co(II), Cr(III), Cu(II), Fe(III), Mn(II), Ni(II), Pb(II), Ti(IV), and Zn(II). The metal ions adsorbed could be readily desorbed using 0.1 or 0.5 mol L(-1) HNO(3). The chelating fiber containing carboxymethylated polyallylamine was available for the separation of some metal ions in synthetic wastewater containing a large amount of Na(2)SO(4). The wet spinning technique using a solution containing a base polymer and a polymer ligand was quite simple and effective and would be applicable for preparing various chelating fibers.

A solid phase extraction using a chelate resin immobilizing carboxymethylated pentaethylenehexamine for separation and preconcentration of trace elements in water samples.

A chelate resin immobilizing carboxymethylated pentaethylenehexamine (CM-PEHA resin) was prepared, and the potential for the separation and preconcentration of trace elements in water samples was evaluated through the adsorption/elution test for 62 elements. The CM-PEHA resin could quantitatively recover various elements, including Ag, Cd, Co, Cu, Fe, Ni, Pb, Ti, U, and Zn, and rare earth elements over a wide pH range, and also Mn at pH above 5 and V and Mo at pH below 7. This resin could also effectively remove major elements, such as alkali and alkaline earth elements, under acidic and neutral conditions. Solid phase extraction using the CM-PEHA resin was applicable to the determination of 10 trace elements, Cd, Co, Cu, Fe, Mn, Mo, Ni, Pb, V, and Zn, in certified reference materials (EnviroMAT EU-L-1 wastewater and ES-L-1 ground water) and treated wastewater and all elements except for Mn in surface seawater using inductively coupled plasma atomic emission spectrometry. The detection limits, defined as 3 times the standard deviation for the procedural blank using 500 mL of purified water (50-fold preconcentration, n=8), ranged from 0.003 microg L(-1) (Mn) to 0.28 microg L(-1) (Zn) as the concentration in 500 mL of solution.