Discarded micro/nano-plastic inputs into the environment are emerging global concerns. Yet the quantification of micro/nanoplastics in complex environmental matrices is still a major challenge, notably for soluble ones. We herein develop in-laboratory built nanostructures (zinc oxide, titanium oxide and cobalt) coupled to mass spectrometry techniques, for picogram quantification of micro/nanoplastics in water and snow matrices, without sample pre-treatment. In parallel, an ultra-trace quantification method for micro/nanoplastics based on nanostructured laser desorption/ionization time-of-flight mass spectrometry (NALDI-TOF-MS) is developed. The detection limit is ∼5 pg for ambient snow. Soluble polyethylene glycol and insoluble polyethylene fragments were observed and quantified in fresh falling snow in Montreal, Canada. Complementary physicochemical studies of the snow matrices and reference plastics using laser-based particle sizers, inductively coupled plasma tandem mass spectrometry, and high-resolution scanning/transmission electron microscopy, produced consistent results with NALDI, and further provided information on morphology and composition of the micro/nano-plastic particles. This work is promising as it demonstrates that a wide range of recyclable nanostructures, in-laboratory built or commercial, can provide ultra-trace capability for quantification for both soluble polymers and insoluble plastics in air, water and soil. It may thereby produce key missing information to determine the fate of micro/nanoplastics in the environment, and their impacts on human health.

Titanium dioxide nanoparticles (TiO₂NPs) application in variety of commercial products would likely release these NPs into the environment. The interaction of TiO₂NPs with terrestrial plants upon uptake can disturb plants functional traits and can also transfer to the food chain members. In this study, we investigated the impact of TiO₂NPs on wheat (Triticum aestivum L.) plants functional traits, primary macronutrients assimilation, and change in the profile of bio-macromolecule. Moreover, the mechanism of biochar-TiO₂NPs interaction, immobilization, and tissue accumulation to cell translocation of NPs in plants was also explored. The results indicated that the contents of Ti in wheat tissues was reduced about 3-fold and the Ti transfer rate (per day) was reduced about 2 fold at the 1000 mg L⁻¹ exposure level of TiO₂NPs in biochar amended exposure medium. Transmission electron microscopy (TEM) with elemental mapping confirmed that Ti concentrated in plant tissues in nano-form. The interactive effect of TiO₂NPs + biochar amendment on photosynthesis related and gas exchange traits was observed at relatively low TiO₂NPs exposure level (200 mg L⁻¹), which induced the positive impact on wheat plants proliferation. TiO₂NPs alone exposure to wheat also modified the plant’s bio-macromolecules profile with the reduction in the assimilation of primary macronutrients, which could affect the food crop nutritional value and quality. X-ray photoelectron spectroscopy (XPS) chemical analysis of biochar + TiO₂NPs showed an additional peak, which indicated the binding interaction of NPs with biochar. Moreover, Fourier-transform infrared (FTIR) spectroscopy confirmed that the biochar carboxyl group is the main functionality involved in the bonding process with TiO₂NPs. These findings will help for a mechanistic understanding of the role of biochar in the reduction of NPs bioavailability to primary producers of the terrestrial environment.

The combined use of nano-TiO₂ with cementitious materials offers an environmentally-friendly way to combat the air pollution problem. However, a trade-off between a high efficiency and a robust weathering resistance has often to be made for most of the attempted nano-TiO₂ incorporation methods. This paper developed a simple and effective “spraying” method to coat nano-TiO₂ particles on the surface of concrete surface layers (CSL). The results showed that the NOₓ removal rate of the samples increased with an increase in both the concentrations of nano-TiO₂ solutions and the number of times of the spraying action. And the conditions for preparation of the Spray AB (the CSL were first sprayed with the 30 g L⁻¹ TiO₂-solution 20 times, followed by mechanical compaction, and for another 20 times after the compaction) were found to be optimal in terms of NOₓ removal performance and weathering resistance. The Spray AB was superior to the 5% TiO₂-intermixed samples with respect to photocatalytic NOₓ removal ability. Compared with TiO₂-dip-coated samples, the Spray AB samples had better and robust weathering resistance. A case study on the factory-fabricated green Eco-blocks (produced by the laboratory-developed spray method and the conventional intermix method) was performed. Examination and comparison on their respective photocatalytic NOₓ removal further verified the advantages of the spray method over the intermix method.

The treatment of industrial waste and harmful bacteria is an important topic due to the release of toxins from the industrial pollutants that damage the water resources. These harmful sources frighten the life of every organism which was later developed as the carcinogenic and mutagenic agents. Therefore, the current study focuses on the breakdown or degradation of 4-chlorophenol and the antibacterial activity against Escherichia coli (E. coli). As a well-known catalyst, pure titanium-di-oxide (TiO₂) had not shown the photocatalytic activity in the visible light region. Hence, band position of TiO₂ need to be shifted to bring out the absorption in the visible light region. For this purpose, the n-type TiO₂ nanocrystalline material's band gap got varied by adding different ratios of p-type CuO. The result had appeared in the formation of p (CuO) – n (TiO₂) junction synthesized from sol-gel followed by chemical precipitation methods. The optical band gap value was determined by Kubelka-Munk (K-M) plot through UV–Vis diffusive reflectance spectroscopy (DRS). Further, the comprehensive mechanism and the results of photocatalytic and antibacterial activities were discussed in detail. These investigations are made for tuning the TiO₂ catalyst towards improving or eliminating the existing various environmental damages.

The present study aimed to assess the toxicity of seven UV-filters: zinc oxide nanoparticles (nZnO, particle size <100 nm), titanium dioxide nanoparticles (nTiO₂, primary particle size 21 nm), 2-ethylhexyl-4-methoxycinnamate (EHMC), 4-methylbenzylidene camphor (4-MBC), avobenzone (AVO), octocrylene (OCTO) and benzophenone-3 (BP-3) on three species: Aliivibrio fischeri (inhibition of bioluminescence), Phaeodactylum tricornutum (growth inhibition) and Ficopomatus enigmaticus (larval development success). Results showed nTiO₂ to be the most toxic for P. tricornutum (EC₅₀ 0.043 mg L⁻¹), while no effect was observed in A. fischeri and F. enigmaticus. EHMC was the most toxic to A. fischeri (EC₅₀ 0.868 mg L⁻¹ (15 min) and 1.06 mg L⁻¹ (30 min)) and the second most toxic to P. tricornutum. For F. enigmaticus, the lowest percentages of correct development resulted from 4-MBC exposure, with EC₅₀ of 0.836 mg L⁻¹. Overall, AVO induced low toxicity to every assessed species and OCTO was the least toxic for F. enigmaticus larvae. Considering the results obtained for F. enigmaticus, further larval development assays were performed with nZnO and EHMC under different light (light vs darkness) and temperature (20 and 25 °C) conditions, showing higher percentages of correct development at 25 °C, independently on light/darkness conditions. Under different temperature and photoperiod conditions, nZnO was more toxic than EHMC. Overall, nZnO and EHMC were among the most toxic UV filters tested and, when testing the effects of these UV-filters with temperature the results highlight that the impacts are liable to be lessened at higher temperatures (25 °C compared with 20 °C), in the case of this estuarine polychaete species. Nevertheless, further experiments are necessary to describe the effects of these two UV-filters at different organization levels, to study the toxicity of eventual degradation by-products and to provide more information on the combination of different stressors.

Amongst other threats, the world’s oceans are faced with man-made pollution, including an increasing number of microparticulate pollutants. Sponges, aquatic filter-feeding animals, are able to incorporate fine foreign particles, and thus may be a potential bioindicator for microparticulate pollutants. To address this question, 15 coral reef demosponges sampled around Bangka Island (North Sulawesi, Indonesia) were analyzed for the nature of their foreign particle content using traditional histological methods, advanced light microscopy, and Raman spectroscopy. Sampled sponges accumulated and embedded the very fine sediment fraction (<200 μm), absent in the surrounding sand, in the ectosome (outer epithelia) and spongin fibers (skeletal elements), which was confirmed by two-photon microscopy. A total of 34 different particle types were identified, of which degraded man-made products, i.e., polystyrene, particulate cotton, titanium dioxide and blue-pigmented particles, were incorporated by eight specimens at concentrations between 91 and 612 particle/g dry sponge tissue. As sponges can weigh several hundreds of grams, we conservatively extrapolate that sponges can incorporate on average 10,000 microparticulate pollutants in their tissue. The uptake of particles, however, appears independent of the material, which suggests that the fluctuation in material ratios is due to the spatial variation of surrounding microparticles. Therefore, particle-bearing sponges have a strong potential to biomonitor microparticulate pollutants, such as microplastics and other degraded industrial products.

Nanoparticulate mineral UV filters, such as titanium dioxide (TiO₂) nanocomposites, are being increasingly used in sunscreens as an alternative to organic UV filters. However, there is still a lack of understanding regarding their fate and behavior in aquatic environments and potential environmental impacts after being released from a bather’s skin during recreational activities. In this work, we assessed the release, fate, and transformation of two commercial nanocomposite TiO₂ UV filters, one hydrophobic and one hydrophilic, in ultrapure water and simulated fresh- and seawater. The hydrophobic TiO₂ nanocomposite, T-SA, was coated with a primary Al₂O₃ photopassivation layer and a secondary stearic acid layer, while the hydrophilic TiO₂ nanocomposite, T-SiO₂, was coated with a single SiO₂ photopassivation layer. The influence of the sunscreen formulation was examined by dispersing the TiO₂ nanocomposites in their typical continuous phase (i.e., oil for T-SA and water for T-SiO₂) before introduction into the aqueous system. After 48 h of aqueous aging and 48 h of settling, 88–99% of the hydrophobic T-SA remained floating on top of the water column in all aqueous systems. On the other hand, 100% of the hydrophilic T-SiO₂ settled out of the water column in the fresh- and seawaters. With respect to the photopassivation coatings, no loss of the T-SA Al₂O₃ layer was detected after aqueous aging, but 99–100% dissolution of the SiO₂ layer on the T-SiO₂ nanocomposite was observed after 48 h in the fresh- and seawaters. This dissolution left behind T-SiO₂ by-products exhibiting a photocatalytic activity similar to that of bare rutile TiO₂. Overall, the results demonstrated that the TiO₂ surface coating and sunscreen formulation type drive environmental behavior and fate and that loss of the passivation layer can result in potentially harmful, photoactive by-products. These insights will help guide regulations and assist manufacturers in developing more environmentally safe sunscreens.

An increasing production and use of titanium dioxide nanoparticles (TiO₂ NPs) pose a huge threat to phytoplankton since they are largely released into aquatic environments, which represent a sink for TiO₂ NPs. However, toxicity and protective mechanisms of cyanobacteria in response to TiO₂ NPs remain elusive. Here we investigated toxic effects of two sizes of TiO₂ NPs (50 and 10 nm) and one bulk TiO₂ (200 nm) on a cyanobacterium, Synechocystis sp. and their possible protective mechanisms. We found that 10 nm TiO₂ NPs caused significant growth and photosynthesis inhibition in Synechocystis sp. cells, largely reflected in decreased growth rate (38%), operational PSII quantum yields (40%), phycocyanin (51%) and allophycocyanin (63%), and increased reactive oxygen species content (245%), superoxide dismutase activity (46%). Also, transcriptomic analysis of Synechocystis sp. exposure to 10 nm TiO₂ NPs showed the up-regulation of D1 and D2 protein genes (psbA and psbD), ferredoxin gene (petF) and F-type ATPase genes (e.g., atpB), and the down-regulation of psbM and psb28-2 in PS II. We further proposed a conceptual model to explore possible toxic and protective mechanisms for Synechocystis sp. under TiO₂ nanoparticle exposure. This study provides mechanistic insights into our understanding of Synechocystis sp. responses to TiO₂ NPs. This is essential for more accurate environmental risk assessment approaches of nanoparticles in aquatic ecosystems by governmental environmental agencies worldwide.

Concerns about the environmental and human health implications of TiO₂ nanoparticles (nTiO₂) are growing with their increased use in consumer and industrial products. Investigations of the underlying molecular mechanisms of nTiO₂ tolerance in organisms will assist in countering nTiO₂ toxicity. In this study, the countermeasures exhibited by the slime mold Physarum polycephalum macroplasmodium against nTiO₂ toxicity were investigated from a physiological, transcriptional, and metabolic perspective. The results suggested that the countermeasures against nTiO₂ exposure include gene-associated metabolic rearrangements in cellular pathways involved in amino acid, carbohydrate, and nucleic acid metabolism. Gene-associated nonmetabolic rearrangements involve processes such as DNA repair, DNA replication, and the cell cycle, and occur mainly when macroplasmodia are exposed to inhibitory doses of nTiO₂. Interestingly, the growth of macroplasmodia and mammal cells was significantly restored by supplementation with a combination of responsive metabolites identified by metabolome analysis. Taken together, we report a novel model organism for the study of nTiO₂ tolerance and provide insights into countermeasures taken by macroplasmodia in response to nTiO₂ toxicity. Furthermore, we also present an approach to mitigate the effects of nTiO₂ toxicity in cells by metabolic intervention.

Herein, we report the optimization of nitrogen (N) doping in TiO₂ nanotubes to achieve the enhanced photocatalytic efficiencies in degradation of dye and H₂ gas evolution under solar light exposure. TiO₂ nanotubes have been produced via hydrothermal process and N doping has been tuned by varying the concentration of urea, being the source for N, by solid-state dispersion process. The structural analysis using XRD showed the characteristic occupancy of N into the structure of TiO₂ and the XPS studies showed the existence of Ti–N–Ti network in the N-doped TiO₂ nanotubes. The obtained TEM images showed the formation of 1D tube-like structure of TiO₂. Diffuse reflectance UV–Vis absorption spectra demonstrated that the N-doped TiO₂ nanotubes can efficiently absorb the photons of UV–Vis light of the solar light. The optimized N-doped TiO₂ nanotubes (TiO₂ nanotubes vs urea @ 1:1 ratio) showed the highest degradation efficiency over methyl orange dye (∼91% in 90 min) and showed the highest rate of H₂ evolution (∼19,848 μmol h⁻¹.g⁻¹) under solar light irradiation. Further, the recyclability studies indicated the excellent stability of the photocatalyst for the durable use in both the photocatalytic processes. The observed efficiency was ascribed to the optimized doping of N-atoms into the lattices of TiO₂, which enhanced the optical properties by forming new energy levels of N atoms near the valence band maximum of TiO₂, thereby increased the overall charge separation and recombination resistance in the system. The improved reusability of photocatalyst is attributed to the doping-induced structural stability in N-doped TiO₂. From the observed results, it has been recognized that the established strategy could be promising for synthesizing N-doped TiO₂ nanotubes with favorable structural, optical and photocatalytic properties towards dye degradation and hydrogen production applications.