Subterranean transport of microplastics as evidenced in karst springs and their characterization using Raman spectroscopy.

The increasing use of plastic materials has led to accumulation of large amounts of plastic waste in environment and a global challenge to be tackled with. The natural process of macro-plastics aging generates a multitude of secondary microplastic fragments accumulating in all areas of the planet. The pollution with microplastics of large water bodies, such as rivers, seas and oceans was already proven, but the presence of microplastics even in karst spring water was not reported yet. In this study, Raman micro-spectroscopy was used to confirm the presence of microplastics in the spring water samples collected from two rural karst springs in the Apuseni Mountains (Țarina and Josani), North-Western Romania. Two sets of water samples of 1000 L collected in spring time 2021 and one in autumn 2021 were filtered and analyzed. Using the Python programming language and combining two separate Raman databases, one for plastics and the other for pigments, we established a customized database to unambiguously identify the type of plastic and pigment present in the discovered micro-fragments. The generated reference pigment-plastic spectra were compared to those of potential microplastics found on filters and Pearson's coefficient was used to measure the level of similarity. The presence of microplastics in karst spring waters was confirmed and a quantitative estimation expressed as number of fragments or fibers per liter was 0.034 in Josani and 0.06 in Țarina karst spring. Five months later sampling (autumn 2021) revealed 0.05 microplastics per liter. The spectral results revealed that most microplastics found were dominated by polyethylene terephthalate (PET), followed by polypropylene and interestingly, abundant blue micro-fragments were identified according to their copper phthalocyanine pigments (pigment Blue 15) or indigo carmine (pigment Blue 63) characteristic spectral fingerprints, which surpassed the inherent spectral background level characteristic for the Raman spectra of naturally contaminated waste micro-samples. Their origin in mountain karst spring waters and potential decrease in time is discussed.

A simple approach for coffee-ring suppression yielding homogeneous drying patterns of ZnO and TiO2 nanoparticles.

Evaporation-induced self-assembly in colloidal droplets is a method for organising nanoparticles on substrates, with various resulting patterns. The coffee-ring pattern is among the most common ones, but its non-uniformity limits its applicability, which led to efforts for developing coffee-ring suppression strategies. Considering the wide applicability of ZnO and TiO2 nanoparticles, there is a high demand for practical means to deposit them as uniform films. Here, we present a simple approach for obtaining highly uniform thin films of ZnO and TiO2 nanoparticles by drop-coating in ambient conditions, without using surfactants or other surface chemistry modifications. Disc-like films were obtained via a restricted evaporation achieved by covering the droplets with a lid during drying, seconded by the relatively high sedimentation rate of these nanoparticles. To better understand the assembly mechanism, the influence of suspension concentration, type and temperature of the substrate, droplet volume, colloid type, and evaporation rate were studied. The method allows preparing disc-like nanoparticle films with a good control over their diameter and thickness, onto different kinds of substrates (glass, Si, polyethylene terephthalate, polystyrene). By fabricating both two-dimensional lattices and custom disc patterns we highlight the versatility of this drop-coating method and its potential for, e.g., automatized serial production processes.

Zinc oxide nanostructures for fluorescence and Raman signal enhancement: a review.

Since the initial discovery of surface-enhanced Raman scattering (SERS) and surface-enhanced fluorescence (SEF), these techniques have shown huge potential for applications in biomedicine, biotechnology, and optical sensors. Both methods rely on the high electromagnetic fields created at locations on the surface of plasmonic metal nanoparticles, depending on the geometry of the nanoparticles, their surface features, and the specific location of analyte molecules. Lately, ZnO-based nanostructures have been exploited especially as SERS substrates showing high enhancement factors and increased charge transfer effect. Additionally, applications focused on enhancing the fluorescence of analyte molecules as well as on tuning the photoluminescence properties of ZnO nanostructures through combination with metal nanoparticles. This review covers the major recent results of ZnO-based nanostructures used for fluorescence and Raman signal enhancement. The broad range of ZnO and ZnO-metal nanostructures synthesis methods are discussed, highlighting low-cost methods and the recyclability of ZnO-based nanosubstrates. Also, the SERS signal enhancement by ZnO-based nanostructures and the influences of lattice defects on the SERS signal are described. The photoluminescence enhancement of ZnO in the presence of noble metal nanoparticles and the molecular fluorescence enhancement in the presence of ZnO alone and in combination with metal nanoparticles are also reviewed.

Raman technology application for plastic waste management aligned with FAIR principle to support the forthcoming plastic and environment initiatives.

Plastic production and worldwide use of plastic materials have continued to rise due to their convenience and excellent marketing advantages. This is generating an environmental crisis and global scale pollution which is one of the greatest threats to our planet. One of the best responses could be accomplished by improving recycling and waste management strategies. In this paper we conducted Raman analyses of representative stock of plastics aged in terrestrial or aquatic environments spanning in age up to 15 years. We aimed to establish any potential influence of the aging conditions on the Raman signature of specific plastics. This information is further used to build up a Raman logic gate for automatic sorting of plastic waste recovered from environment. Pigments and aging introduced indeed small changes in the Raman signature of the respective plastics. However, we were able to identify unique spectral ranges characteristic for the main plastic types and intensity threshold of fingerprint bands sufficiently strong for building robust Raman barcodes for sorting. Waste plastics Raman data handling and the proposed methodology for sorting complies with the FAIR (Findability, Accessibility, Interoperability and Reusability) principles of scientific data, being useful for researchers, policymakers and stakeholders. Our spectral characterization of solid plastic waste comes in support of improved waste plastic management and could have economic and environmental positive impact.