Validated method for polystyrene nanoplastic separation in aqueous matrices by asymmetric-flow field flow fraction coupled to MALS and UV-Vis detectors.

Plastics with nanosize (nanoplastics, NPLs) must be characterized, since they can be toxic or act as carriers of organic and inorganic pollutants, but there is a lack of reference materials and validated methods in the nanosize range. Therefore, this study has focused on the development and validation of a separation and size characterization methodology of polystyrene latex nanospheres, by using an asymmetric-flow field flow fraction system coupled to multi-angle light scattering and ultraviolet-visible detectors (AF4-MALS-UV). Hence, this work presents a fully validated methodology in the particle size range 30 to 490 nm, with bias between 95 and 109%, precision between 1 and 18%, LOD and LOQ below 0.2 and 0.3 µg respectively, except for 30-nm standard, for both detectors, and showing stable results for 100 analyses.

Tooth whitening effects on dental enamel, oxidation or reduction? Comparison of physicochemical alterations in bovine enamel using Synchrotron-based Micro-FTIR.

OBJECTIVES: To compare the side effects of typical whitening treatments (by means of oxidation) compared to the new treatment developed by the authors through reduction. The aim is to provide information about the chemical interactions of the encapsulated reductant agent (metabisulfite, MBS) with the enamel structure compared with carbamide peroxide (CP) and to study their penetration in the hydroxyapatite (HAP) and the changes produced in the mineral and its hardness. METHODS: Chemical imaging is performed by synchrotron-based micro Fourier transformed infrared spectroscopy (SR-µFTIR). Continuous Stiffness Measurements (CSM) were used to determine the depth reached by the treatments in order to delimitate the area of study. RESULTS: The SR-µFTIR studies showed that MBS treatments softened the first 10 µm of enamel, as happens in the initial stages of tooth decay. Principal component analysis (PCA) showed that the main differences between treatments were found in the intensity of the ν3 PO43- peak related to tooth demineralization. CP and MBS promoted different changes in the HAP mineral, observed as opposite shifts of the peak: CP shortened the P-O bond while MBS seemed to elongate it. Moreover, MBS promoted the loss of carbonates while CP did not, which is probably related to the solution's pH. When comparing MBS and MBS Liposomes, it was observed how liposomes favoured the diffusion of MBS to inner layers, since the effects of MBS were observed in deeper enamel. Thus, the encapsulated MBS whitening effect is highly improved in terms of time when compared to MBS alone or CP. SIGNIFICANCE: The obtained results indicated that using oxidizing (CP) or reducing (MBS) treatments, promote different HAP mineral changes, and that liposomes favour the diffusion of MBS into the enamel. It is the first time that synchrotron light is used to map the bovine incisor's enamel chemically, and to determine the effect of a whitening treatment in terms of chemical HAP modifications, and the extent in deep of these effects.

Calcium oxalate kidney stones, where is the organic matter?: A synchrotron based infrared microspectroscopy study.

Kidney stones are collections of microcrystals formed inside the kidneys, which affect 6% to 12% of the population worldwide, with an increasing recurrence (50%-72%) after the first episode. The most abundant type is calcium oxalate (66%), described as monohydrated (COM) and dihydrated (COD). An issue in their chemistry is the transformation process of the metastable specie (COD) into the stable one, which is chemically, and in appearance, monohydrated. Since the origin of these species is different, it is important to differentiate between the transformation stage (and what stabilize COD) to understand the physiopathology and prevent the patients' recurrence. This work focuses on the organic matter distribution along these nephroliths by synchrotron radiation-based infrared microspectroscopy. Differences in the asymmetric stretching of the aliphatic hydrocarbons suggest that lipids may participate in the stabilization of COD and as inhibitors of COM formation/development; however, the presence of proteins in the nucleus could indicate a promoting role.

Physico-chemical characterization of playground sand dust, inhalable and bioaccessible fractions.

Dust is a mixture of natural and anthropogenic particles originated from multiple sources, which can represent an hazard for human health. Playgrounds are a site of particularly concern, due to sand dust ingestion by toddlers and inhalation. In this study, 37 sands used in public playgrounds in the city of Barcelona were physico-chemically characterized also in relation to routine maintenance activities such as disinfection and sand renewal. The analyzed sands show a felsic mineralogy dominated by Na-feldspar, quartz, and, to a lesser extent, K-feldspar, with minor amounts of clay minerals, carbonates and hematite. Particle fractions below 10, 2.5 and 1 µm represent, on average, 0.65%, 0.17% and 0.07% of bulk volume, respectively, although, due to the human grinding, these initial fractions increased every year by a 18%, 5% and 2% respectively. Disinfection of sands effectively reduced only the NH4+ concentration, among inorganic species. The average metal content was anthropogenically enriched, with respect to the upper continental crust, only for Sb and As. Both elements show high spatial variation indicating local sources such as road traffic for Sb (contributing mostly to the total concentration), and industry for As (also contributing with highly bioaccessible Sb, Cu and Zn). A clear inverse relationship between total concentrations of some elements and their leachable (Sb) and bioaccessible (Sb and Cr) fractions is observed. The most bioaccessible elements were Ca > Ni > Cu > Sr > Cd > Pb, all above the 25% of the total concentration. Bioaccessibility was higher for the carbonate-bearing particles and for the anthropic emitted metals (>50% of Ba, Cu, K, Pb and Zn).