Comparing the effects of pristine and UV-VIS aged microplastics: Behavioural response of model terrestrial and freshwater crustaceans.

Physico-chemical properties of microplastics (MPs) change during weathering in the environment. There is a lack of knowledge about the effects of such environmentally relevant MPs on organisms. We investigated: 1) the physico-chemical changes of MPs due to UV-VIS weathering, and 2) compared the effect of pristine and aged MPs on the behaviour of the water flea Daphnia magna and terrestrial crustacean Porcellio scaber. Dry powders of MPs were produced from widely used polymer types: disposable three-layer polypropylene (PP) medical masks (inner, middle and outer), polyester textile fibres, car tires and low-density polyethylene (LDPE) bags and were subjected to accelerated ultraviolet-visible (UV-VIS) ageing. Our results show that the extent of transformation depends on the type of polymer, with PP showing the most changes, followed by LDPE, textile fibres and tire particles. Obvious fragmentation was observed in PP and textile fibres. In the case of PP, but not polyester textile fibres, changes in FTIR spectra and surface properties were observed. Tire particles and LDPE did not change in size, but clear changes were observed in their FTIR spectra. Most MPs, aged and pristine, did not affect the swimming of daphnids. The only effect observed was a significant increase in path length and swimming speed for the pristine tire particles when the recording was done with particles remaining in the wells. After transfer to a clean medium, this effect was no longer present, suggesting a physical rather than chemical effect. Similarly, woodlice showed no significant avoidance response to the MPs tested, although there was a noticeable trend to avoid soils contaminated with pristine polyester textile fibers and preference towards the soils contaminated with aged MP of the middle mask layer. Overall, the apparent changes in physico-chemical properties of MPs after accelerated ageing were not reflected in their effects on woodlice and daphnids.

The Microstructural Reconstruction of Variously Sintered Ni-SDC Cermets Using Focused Ion Beam Scanning Electron Microscopy Nanotomography.

This work focuses in-depth on the quantitative relationships between primary first-order microstructural parameters (i.e., volume fractions of various phases and particle size distribution) with the more complex second-order topological features (i.e., connectivity of phases, three-phase boundary length (TPBL), interfacial areas, or tortuosity). As a suitable model material, a cermet nickel/samaria-doped ceria (Ni-SDC) is used as an anode in a solid oxide fuel cell (SOFC). A microstructure description of nano-sized Ni-SDC cermets, fabricated at various sintering conditions from 1100 °C to 1400 °C, was performed using FIB-SEM nanotomography. The samples were serially sectioned employing a fully automated slicing procedure with active drift correction algorithms and an auto-focusing routine to obtain a series of low-loss BSE images. Advanced image processing algorithms were developed and applied directly to image data volume. The microstructural-topological relationships are crucial for the microstructure optimisation and, thus, the improvement of the corresponding electrode performance. Since all grains of individual phases (Ni, SDC, or pores) did not percolate, special attention was given to the visualisation of the so-called active TPBL. Based on the determined microstructure characteristics of the prepared Ni-SDC cermets, including simulations of gas flow and pressure drop, thermal treatment at 1200 °C was recognised as the most appropriate sintering temperature.

High-Entropy Oxides: A New Frontier in Photocatalytic CO2 Hydrogenation.

Herein, we investigate the potential of nanostructured high-entropy oxides (HEOs) for photocatalytic CO2 hydrogenation, a process with significant implications for environmental sustainability and energy production. Several cerium-oxide-based rare-earth HEOs with fluorite structures were prepared for UV-light driven photocatalytic CO2 hydrogenation toward valuable fuels and petrochemical precursors. The cationic composition profoundly influences the selectivity and activity of the HEOs, where the Ce0.2Zr0.2La0.2Nd0.2Sm0.2O2-δ catalyst showed outstanding CO2 activation (14.4 molCO kgcat-1 h-1 and 1.27 molCH3OH kgcat-1 h-1) and high methanol and CO selectivity (7.84% CH3OH and 89.26% CO) under ambient conditions with 4 times better performance in comparison to pristine CeO2. Systematic tests showed the effect of a high-entropy system compared to midentropy oxides. XPS, in situ DRIFTS, as well as DFT calculation elucidate the synergistic impact of Ce, Zr, La, Nd, and Sm, resulting in an optimal Ce3+/Ce4+ ratio. The observed formate-routed mechanism and a surface with high affinity to CO2 reduction offer insights into the photocatalytic enhancement. While our findings lay a solid foundation, further research is needed to optimize these catalysts and expand their applications.

Insights into the shape-dependent effects of polyethylene microplastics on interactions with organisms, environmental aging, and adsorption properties.

The shape-dependent effects of microplastics have been studied in the context of ingestion but have not been considered in other environmental processes. Therefore, we investigated how the shape of polyethylene microplastics (spheres, fragments, and films) affects interactions with plants, aging, and their adsorption properties. The shape had no effect on the growth rate and chlorophyll content of duckweed Lemna minor, but the fragments strongly adhered to the plant biomass and reduced the root length. The adsorption process of the model organic compound (methylene blue dye) was described by the same kinetic model for all shapes-the experimental data best fit the pseudo-second order model. However, twice as much methylene blue was adsorbed on films as on fragments and spheres. During environmental aging, most biofilm developed on films. The biofilm on spheres contained significantly less photosynthetic microorganisms, but twice as much extracellular polymeric substances (EPS) as on fragments and films. This suggests that the attachment of microorganisms to spherical particles is limited and therefore more intensive production of EPS is required for stable biofilm formation. From the results of this study, it is evident that the shape of microplastics significantly affects not only ecotoxicity but also other environmentally relevant processes.

Interactions between titanium dioxide nanoparticles and polyethylene microplastics: Adsorption kinetics, photocatalytic properties, and ecotoxicity.

The present study investigated the adsorption mechanism of titanium dioxide nanoparticles (nTiO2) on polyethylene microplastics (MPs) and the resulting photocatalytic properties. This effort was supported by ecotoxicological assessments of MPs with adsorbed nTiO2 on the immobility and behaviour of Daphnia magna in presence and absence of UV irradiation. The results showed that nTiO2 were rapidly adsorbed on the surface of MPs (72% of nTiO2 in 9 h). The experimental data fit well with the pseudo-second order kinetic model. Both suspended nTiO2 and nTiO2 immobilized on MPs exhibited comparable photocatalytic properties, with the latter showing a lower effect on Daphnia mobility. A likely explanation is that the suspended nTiO2 acted as a homogeneous catalyst under UV irradiation and generated hydroxyl radicals throughout the test vessel, whereas the nTiO2 adsorbed on MPs acted as a heterogeneous catalyst and generated hydroxyl radicals only locally and thus near the air-water interface. Consequently, Daphnia, which were hiding at the bottom of the test vessel, actively avoided exposure to hydroxyl radicals. These results suggest that the presence of MPs can modulate the phototoxicity of nTiO2 - at least the location at which it is active - under the studied conditions.

Exploring the impacts of microplastics and associated chemicals in the terrestrial environment - Exposure of soil invertebrates to tire particles.

Abrasion of tire wear is one of the largest sources of microplastics to the environment. Although most tire particles settle into soils, studies on their ecotoxicological impacts on the terrestrial environment are scarce. Here, the effects of tire particles (<180 µm) on three ecologically relevant soil invertebrate species, the enchytraeid worm Enchytraeus crypticus, the springtail Folsomia candida and the woodlouse Porcellio scaber, were studied. These species were exposed to tire particles spiked in soil or in food at concentrations of 0.02%, 0.06%, 0.17%, 0.5% and 1.5% (w/w). Tire particles contained a variety of potentially harmful substances. Zinc (21 900 mg kg-1) was the dominant trace element, whilst the highest concentrations of the measured organic compounds were detected for benzothiazole (89.2 mg kg-1), pyrene (4.85 mg kg-1), chlorpyrifos (0.351 mg kg-1), HCB (0.134 mg kg-1), methoxychlor (0.116 mg kg-1) and BDE 28 (0.100 mg kg-1). At the highest test concentration in soil (1.5%), the tire particles decreased F. candida reproduction by 38% and survival by 24%, and acetylcholinesterase (AChE) activity of P. scaber by 65%, whilst the slight decrease in the reproduction of E. crypticus was not dose-dependent. In food, the highest test concentration of tire particles reduced F. candida survival by 38%. These results suggest that micro-sized tire particles can affect soil invertebrates at concentrations found at roadsides, whilst short-term impacts at concentrations found further from the roadsides are unlikely.

An extensive characterization of various environmentally relevant microplastics - Material properties, leaching and ecotoxicity testing.

Microplastics in the environment occur in different sizes and shapes and are made of various polymers. Therefore, they also considerably differ in their properties and ecotoxicity. However, the majority of microplastics research uses pre-made spherical microplastics, which practically do not exist in the environment. Our work focused on a comprehensive study of six different types of microplastic that were prepared to simulate common microplastics found in the environment. All types of microplastics where chemically and physically characterized using Fourier-transform infrared spectroscopy, thermal analysis, field-emission scanning electron microscopy, optical microscopy and laser diffraction analysis. The specific surface area was determined using the BET method. Furthermore, effects of microplastics and microplastic leachates on a common duckweed (Lemna minor) were evaluated. All tested microplastics did not affect specific growth rate and chlorophyll a content in duckweed, while microplastics with a rough surface and sharp edges caused a significant reduction of duckweed root length. Microplastics made of Bakelite also showed an intensive leaching, which increased their ecotoxicity potential. Natural particles used as a control did not have any negative effect on duckweed. Overall, microplastic particles have significantly different ecotoxicity profiles depending on their physico-chemical properties. Therefore, the testing of environmentally relevant particles and their proper characterization, as well as the testing of microplastic leaching properties, is crucial for understanding of microplastics ecotoxicological potential.

An environmental concentration of aged microplastics with adsorbed silver significantly affects aquatic organisms.

Microplastics are very complex pollutants; they can be made of many polymer types and exist in various shapes and sizes. When they enter the environment they are affected by biotic and abiotic factors that cause their properties to change. In this context, the aim of our study was to evaluate the extent to which biofouling affects the properties and toxicity of microplastics. Cosmetic polyethylene microbeads were incubated in stream water for four weeks resulting in biofouling and aging. Subsequently, the changes in properties (sinking, particle size, adsorption, and leaching of model metal - silver) and the microplastics toxicity to daphnids Daphnia magna and duckweed Lemna minor were evaluated. Pristine microplastics did not affect daphnids but they significantly affected the root growth of duckweed. On the other hand, reference natural particles (beech sawdust) did not show any negative effects. We observed significant differences in the properties of aged versus pristine microplastics. When compared to pristine microplastics, aged microplastics adsorbed more silver and the subsequent leaching of silver was more intensive, especially in the medium with an acidic pH. Microplastics with adsorbed silver had a high ecotoxicological potential and at environmentally relevant concentrations affected both daphnids and duckweed. This study suggests that biofouling is an important parameter that affects microplastics properties, pollutant adsorption and release into the environment, and toxicity. Overall, there are significant alterations of the microplastics properties, behaviour, and fate in the environment.

Exploring the impacts of plastics in soil - The effects of polyester textile fibers on soil invertebrates.

Polyester fiber is one of the most abundant types of microplastics in the environment. A major proportion of the fibers entering wastewater treatment plants end up in sewage sludge, which is used as a soil fertilizer in many countries. As their impacts in the terrestrial environment are still poorly understood, we studied the effects of polyester fibers on enchytraeids (Enchytraeus crypticus), springtails (Folsomia candida), isopods (Porcellio scaber) and oribatid mites (Oppia nitens), all playing an important role in soil decomposer food webs. We exposed these invertebrates in the laboratory to short (12 µm-2.87 mm) and long (4-24 mm) polyester fibers, spiked in soil or in food at five concentrations ranging from 0.02% to 1.5% (w/w) and using five replicates. Overall the effects of polyester fibers on the soil invertebrates were slight. Energy reserves of the isopods were slightly affected by both fiber types, and enchytraeid reproduction decreased up to 30% with increasing fiber concentration, but only for long fibers in soil. The low ingestion of long fibers by the enchytraeids suggests that this negative impact arose from a physical harm outside the organism, or from indirect effects resulting from changes in environmental conditions. The short fibers were clearly ingested by enchytraeids and isopods, with the rate of ingestion positively related to fiber concentration in the soil. This study shows that polyester fibers are not very harmful to soil invertebrates upon short-term exposure. However, longer lasting, multigeneration studies with functional endpoints are needed to reveal the possible long-term effects on soil invertebrates and their role in the decomposition process. This study also shows that polyester fibers can enter terrestrial food web via ingestion of fibers by soil invertebrates.

Screening study of four environmentally relevant microplastic pollutants: Uptake and effects on Daphnia magna and Artemia franciscana.

This study investigated four different environmentally relevant microplastic (MP) pollutants which were derived from two facial cleansers, a plastic bag and polyethylene textile fleece. The mean size range of the particles (according to number distribution) was 20-250 µm when measured as a powder and 0.02-200 µm in suspension. In all MP exposures, plastic particles were found inside the guts of D. magna and A. franciscana, but only in the case of daphnids a clear exponential correlation between MP uptake in the gut and the size of the MP was identified. Exposure tests in which the majority of the MP particles were below 100 µm in size also had higher numbers of daphnids displaying evidence of MP ingestion. As the average MP particle size increased, the percentage of daphnids which had MP in their gut decreased. Using a number distribution value to measure particle size when in a suspension is more experimentally relevant as it provides a more realistic particle size than when samples are measured as a powder. Generally, artemias had fewer MP particles in the gut, than the daphnids, which could be explained by their different food size preferences. No acute effects on D. magna were found, but the growth of A. franciscana was affected. We conclude that zooplankton crustacean can ingest various MPs but none of the exposures tested were highly acutely hazardous to the test species. In addition, no delayed lethal effects in a 24 h post-exposure period were found.

Plastic bag and facial cleanser derived microplastic do not affect feeding behaviour and energy reserves of terrestrial isopods.

Current data regarding the effects of microplastic (MP) on terrestrial organisms are very scarce. Isopods play an important role in plant litter decomposition processes and are commonly used test species in terrestrial ecotoxicity studies. Their altered feeding behaviour and energy reserves are established biomarkers of adverse effects upon stressor exposure. For this study we assessed the effects of MP derived from plastic bag film (mean size 183±93µm) and particles from a facial cleanser (mean size 137±51µm) on the terrestrial isopod, Porcellio scaber. Isopods were exposed to MP via feeding on food pellets (4mgg-1 dry weight; 0.4% w w-1) for 14days under laboratory conditions. A control group was exposed to food pellets with no MP added. In line with previously suggested modes of MP action on animal ingestion, we assessed the food ingestion rate, defecation rate, food assimilation rate and efficiency, body mass change, mortality and energy reserves (proteins, carbohydrates, and triglycerides) in the digestive glands (hepatopancreas) of individual isopods. Contrary to our expectations, no effects on either end-point were observed under the given exposure conditions. Further work should be carried out to investigate the potential longer-term effects of such exposure. We conclude that 14days exposure to plastic bag and facial cleanser MP is not severely hazardous to isopods.

The novel crystal structure with Zr6O4(OH)4 core and hydrazine carboxylate ligands, and its thermal properties.

The title compound, [Zr(6)(OH)(4)O(4)(N(2)H(3)COO)(12)] · 14H(2)O, was prepared with a novel multi-step synthetic pathway. The structure contains a Zr(6)(µ(3)-OH)(4)(µ(3)-O(4))(12+) core on which twelve hydrazine carboxylate anions are bound to form neutral coordination molecules. The coordination mode of carboxylate ligand is exclusively N,O-bidentate chelating, which is observed for the first time in this class of compounds. The title compound is also the first example of isolated Zr(IV) oxo clusters with cubic symmetry. The structure is stabilized with an extensive hydrogen bond network between coordination and water molecules, and amongst the solvent water molecules themselves. Thermogravimetric studies have shown that the prepared [Zr(6)(OH)(4)O(4)(N(2)H(3)COO)(12)] · (14)H(2)O decomposed in several consecutive steps characterized by evolution of H(2)O, CO, CO(2), N(2) and H(2), finally yielding ZrO(2). The decomposition mechanism is rather complex and includes the formation of a series of amorphous intermediates.