Towards a reference material for microplastics' number concentration-case study of PET in water using Raman microspectroscopy.

Increasing demand for size-resolved identification and quantification of microplastic particles in drinking water and environmental samples requires the adequate validation of methods and techniques that can be used for this purpose. In turn, the feasibility of such validation depends on the existence of suitable certified reference materials (CRM). A new candidate reference material (RM), consisting of polyethylene terephthalate (PET) particles and a water matrix, has been developed. Here, we examine its suitability with respect to a homogeneous and stable microplastic particle number concentration across its individual units. A measurement series employing tailor-made software for automated counting and analysis of particles (TUM-ParticleTyper 2) coupled with Raman microspectroscopy showed evidence of the candidate RM homogeneity with a relative standard deviation of 12% of PET particle counts involving particle sizes >30 µm. Both the total particle count and the respective sums within distinct size classes were comparable in all selected candidate RM units. We demonstrate the feasibility of production of a reference material that is sufficiently homogeneous and stable with respect to the particle number concentration.

Determination of fluoride content in teas and herbal products popular in Poland.

Purpose: Fluoride level, due to its narrow therapeutical range, must be constantly monitored in beverages, especially in daily-consumed plant infusions. Fluoride is important for prevention of tooth decay and osteoporosis, but its excess leads to fluorosis. Since tea can selectively absorb fluorides from soils, the question arises if a long-term consumption can pose an adverse effect on human health. Methods: Infusions of 33 popular teas (black, green, white, earl grey, pu-erh), tea-like products (rooibos, yerba mate) and herbs (chamomile, mint, nettle, purges, yarrow) available in the Polish market were analyzed with respect to a fluoride level by means of a validated ion-selective electrode method, which is proven to be fast and reliable. Results: Significantly different fluoride concentrations in infusions were observed, with black tea on top, where extraction of fluoride is the highest (average 2.65 mg F-/L, range 0.718-6.029 mg/L). Two-fold higher fluoride contents were measured in infusions made from black tea bags than from leaves (average 3.398 mg/L and 1.529 mg/L, respectively). Green teas released comparable amounts of fluoride as black teas, while in herbal extracts the fluoride content was negligible. Conclusions: The rank with respect to the fluoride concentration in an infusion is as follows: black tea > green tea > earl grey > pu-erh > white tea>>>rooibos, yerba mate, herbal products. Increasing of brewing time results in an increased fluoride content, but the overall content of fluoride in the analyzed infusions of teas and herbs was not high enough to cause a risk of fluorosis, even if left to brew up to 15 min.

Foliar or root exposures to smelter particles: consequences for lead compartmentalization and speciation in plant leaves.

In urban areas with high fallout of airborne particles, metal uptake by plants mainly occurs by foliar pathways and can strongly impact crop quality. However, there is a lack of knowledge on metal localization and speciation in plants after pollution exposure, especially in the case of foliar uptake. In this study, two contrasting crops, lettuce (Lactuca sativa L.) and rye-grass (Lolium perenne L.), were exposed to Pb-rich particles emitted by a Pb-recycling factory via either atmospheric or soil application. Pb accumulation in plant leaves was observed for both ways of exposure. The mechanisms involved in Pb uptake were investigated using a combination of microscopic and spectroscopic techniques (electron microscopy, laser ablation, Raman microspectroscopy, and X-ray absorption spectroscopy). The results show that Pb localization and speciation are strongly influenced by the type of exposure (root or shoot pathway) and the plant species. Foliar exposure is the main pathway of uptake, involving the highest concentrations in plant tissues. Under atmospheric fallouts, Pb-rich particles were strongly adsorbed on the leaf surface of both plant species. In lettuce, stomata contained Pb-rich particles in their apertures, with some deformations of guard cells. In addition to PbO and PbSO4, chemical forms that were also observed in pristine particles, new species were identified: organic compounds (minimum 20%) and hexagonal platy crystals of PbCO3. In rye-grass, the changes in Pb speciation were even more egregious: Pb-cell wall and Pb-organic acid complexes were the major species observed. For root exposure, identified here as a minor pathway of Pb transfer compared to foliar uptake, another secondary species, pyromorphite, was identified in rye-grass leaves. Finally, combining bulk and spatially resolved spectroscopic techniques permitted both the overall speciation and the minor but possibly highly reactive lead species to be determined in order to better assess the health risks involved.

Investigation of inclusions trapped inside Libyan desert glass by Raman microscopy.

Several specimens of Libyan desert glass (LDG), an enigmatic natural glass from Egypt, were subjected to investigation by micro-Raman spectroscopy. The spectra of inclusions inside the LDG samples were successfully measured through the layers of glass and the mineral species were identified on this basis. The presence of cristobalite as typical for high-temperature melt products was confirmed, together with co-existing quartz. TiO(2) was determined in two polymorphic species rutile and anatase. Micro-Raman spectroscopy proved also the presence of minerals unusual for high-temperature glasses such as anhydrite and aragonite.