High-efficiency nanophotocatalysts with large specific surface areas have a broad range of application prospects in the catalytic oxidation treatment of organic pollutants in wastewater. A chemical method was used to synthesize a TiO₂ nanophotocatalyst with a mesoporous structure upon which a rare earth metal (Nd) was deposited, namely Nd-TiO₂-SBA-15 (NTS). The prepared NTS was characterized using X-ray diffractometry, transmission electron microscopy, Raman spectroscopy, and X-ray photoelectron spectrometry. The photocatalytic mechanism was explored using scavenger experiments with photoinduced carriers combined with total organic carbon and UV–Vis measurements. At the same time, the kinetic properties of the NTS photocatalytic degradation of methyl orange (MO) were evaluated. The results showed that the deposition of TiO₂ nanoparticles on the surface of the SBA-15 molecular sieve did not change the mesoporous structure, and Nd was uniformly distributed on the surface of the nanophotocatalyst. The photogenerated holes of the NTS played an important role in the photocatalysis process. In addition, the synthesized NTS had good adaptability in the range of pH 2–10. At pH 4, the reaction rate constant (k) of the MO photocatalytic degradation by NTS was 0.011825 mg·(L·min)⁻¹, and the adsorption equilibrium constant (K) was 0.051359 L mg⁻¹. In addition, the photocatalytic degradation rate of MO by NTS remained above 70%, even when the NTS was recycled four times. The NTS showed a good performance after recycling. This work provides a good foundation for the large-scale application of NTS.

Agricultural soil is one of the main sink for both heavy metals and nanomaterials (NMs). Whether NMs can impact heavy metals uptake or bioaccumulation in plants is unknown. Here, cucumber plants were cultivated in a multi-heavy metals contaminated soil amended with four types of NMs (SiO2, TiO2, ZnS and MoS2) separately for four weeks. Physiological and biochemical parameters were determined to investigate the impact of NMs on plant growth. Inductively coupled plasma mass spectrometry was employed to determine the metal content in plants. Results showed that none of the tested NMs impacted plants biomass, but all the NMs showed different degrees of reduction in heavy metals bioaccumulation in plant roots, stems and leaves. However, four NMs showed different degrees of reduction in macro and micro nutrients uptake. MoS2 decreased the bioaccumulation of heavy metals (As, Cd, Cr, Cu, Ni, Al, Ti and Pb) for 36.4–60.6% and nutrients (Mg, Fe, K, Si and Mn) for 40.1%–50.1% in roots. Exposure to MoS2 NMs also significantly increased 23.4% of Si in leaves, 205.6% and 83.9% of Mo in roots and stems, respectively. In general, the results of this study showed promising potential for NMs to reduce uptake of heavy metals in crop plants, especially MoS2 NMs. However, the negative impacts of perturbing nutrients uptake should be paid attention as well.

Nowadays Cylindrospermopsis raciborskii (C. raciborskii) and the metabolites produced, such as cylindrospermopsin (CYN), pose a serious threat to the ecosystem. Advanced oxidation technologies have been verified as constituting a very promising means to eliminate the risk from harmful algae. But so far little research has focused on the visible-light photocatalytic destruction of C. raciborskii cells and the degradation of their metabolites.In our study, N-doped TiO2 (N-TiO2) was used to degrade C. raciborskii and the degradation was compared with that of the Microcystis aeruginosa (M. aeruginosa). Results showed that although the photodegradation of C. raciborskii was more difficult than that of M. aeruginosa, the treatment with N-TiO2 was still satisfactory. After adding 200 mg/L N-TiO2, C. raciborskii cells (5 × 106 cells/mL) were completely destroyed within 20 h under visible light irradiation, and nearly 90% of the organic matter and CYN in the suspensions were also degraded, thereby markedly improving the water quality.The photocatalytic process starts with damage to the cell membrane resulting in the leakage of internal components. Subsequently, the leaked metabolites were oxidised by the reactive oxidizing species produced by N-TiO2. Thus, the application of N-TiO2 is a promising method for the treatment of C. raciborskii.

Efficient containment and capture of uranium (U(VI)) from aqueous solution is an essential component to ensure socially and environmentally sustainable development. Herein, the three-dimensional graphene/titanium dioxide composite (3D GA/TiO₂) was synthesized and applied as an effective adsorbent to remove U(VI) from wastewater as a function of contact time, temperature, pH and ion strength. The 3D GA/TiO₂ material was characterized by X-ray diffraction, Raman spectroscopy, Fourier-transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The batch experiments results indicated that the adsorption of U(VI) on materials were fitted with the pseudo-second order kinetics and Langmuir models. More specifically, 3D GA/TiO₂ (441.3 mg/g) was observed to outperform the GO (280.0 mg/g), rGO (140.9 mg/g) and TiO₂ (98.5 mg/g) at pH 5.0, which was attributable to the excellent cooperative effects. Furthermore, XPS analyses and DFT calculations confirmed the formation of surface complexes between oxygen-containing group and U(VI) with the U–O bonds length of 2.348 Å (U–O1) and 2.638 Å (U–O2). Meanwhile, the adsorption energy was calculated to be 1.60 eV, which showed a very strong chemisorption during the interaction process. It is believed that the 3D GA/TiO₂ revealed good removal performance for uranyl ions, which showed a great potential application to control the nuclear industrial pollution.

Phagocytosis suppression induced by nanoparticles (NPs) exposure is increasingly reported in marine species. However, the mechanisms underlying this impact remain poorly understood. In order to improve our present understanding of the immunotoxicity of NPs, acute (96 h) TiO2 NP exposure and rescue trials via exogenous supply of Ca2+ were performed in the blood clam, Tegillarca granosa. The results show that the phagocytosis rate, cell viability, and intracellular Ca2+ concentration of haemocytes were significantly suppressed, whereas the intracellular ROS concentration of haemocytes significantly increased upon nTiO2 exposure. Exposure to nTiO2 also led to the significant downregulation of Caspase-3, Caspase-6, apoptosis regulator Bcl-2, Bcl-2-associated X, calmodulin kinase II, and calmodulin kinase kinase II. Furthermore, the toxic impacts of nTiO2 were partially mitigated by the addition of exogenous Ca2+, as indicated by the recovery tendency in almost all the measured parameters. The present study indicates that Ca2+ signaling could be one of the key pathways through which nTiO2 attacks phagocytosis.

The widespread application of commercial TiO₂ NPs inevitably leads to their release into environmental waters through various ways. TiO₂ NPs released into water might be absorbed by and react with periphytic biofilms, which are a kind of aquatic environmental media of important ecological significance, and influence the physiological activity and ecological function of periphytic biofilms. This study investigated the effects of exposure to 1 mg/L and 5 mg/L of TiO₂ NPs on periphytic biofilms cultured indoors. After a 10-day exposure to TiO₂ NPs, the growth (measured by chlorophyll-a content) of microalgal community was inhibited greatly (more than 60%); however, the primary production (indicated by quantum yield) of periphytic biofilms maintained changeless. As for bacteria, TiO₂ NP-exposure increased the bacterial diversity and altered the composition structure. Significant changes were observed in the bacterial communities at the class level, mainly including Alphaproteobacteria, Gammaproteobacteria, Cytophagia, Flavobacteriia, Sphingobacteriia, Synechococcophycideae and Oscillatoriophycideae. The enhancement of metabolic activities (the production of extracellular polymeric substances, especially proteins content increased by 48.51%) of periphytic biofilms was a resistance mechanism to toxicity of NPs. As for extracellular enzyme activities of periphytic biofilms, alkaline phosphatase activity was inhibited (22.43%) after exposed to 5 mg/L of TiO₂ NPs, which posed a threat to phosphorus metabolism of periphytic biofilms. Overall, this study demonstrated that 1 mg/L and 5 mg/L of TiO₂ NPs negatively influenced physiological activities and ecological functions of periphytic biofilms, highlighting that the ecological risks of TiO₂ NPs should be paid attention to.

Evaluating the fate and transport of nanoparticles (NPs) in the subsurface environment is critical for predicting the potential risks to both of the human health and environmental safety. It is believed that numerous environmental factors conspire to control the transport dynamics of nanoparticles, yet the effects of organic phosphates on nanoparticles transport remain largely unknown. In this work, we quantified the transport process of TiO2 nanoparticle (nTiO2) and their retention patterns in water-saturated sand columns under various myo-inositol hexakisphosphate (IHP) or phosphate (Pi) concentrations (0–180 μM P), ferrihydrite coating fractions (λ, 0–30%), ionic strengths (1–50 mM KCl), and pH values (4–8). The transport of nTiO2 was enhanced at increased P concentration due to the enhanced colloidal stability. As compared with Pi at the equivalent P level, IHP showed stronger effect on the electrokinetic properties of nTiO2 particles due to its relatively more negative charge and higher adsorption affinity, thereby facilitating the nTiO2 transport (and thus reduced retention) in porous media. At the IHP concentration of 5 μM, the retention of nTiO2 increased with increasing λ and ionic strength, while decreased with pH. In addition, the retention profiles of nTiO2 showed a typical hyperexponential pattern for most scenarios mainly due to the unfavorable attachment, and can be well described by a hybrid mathematical model that coupled convection dispersion equations with a two-site kinetic model and DLVO theory. These quantitative estimations revealed the importance of IHP on affecting the transport of nTiO2 typically in phosphorus-enriched environments. It provides new insights into advanced understanding of the co-transport of nanoparticles and phosphorus in natural systems, essential for both nanoparticle exposure and water eutrophication.

The N-TiO2/g-C3N4@diatomite (NTCD) composite has been prepared through a simple impregnation method, using titanium tetrachloride as precursor and urea as nitrogen-carbon source. Then the effects of calcination temperature on structure, surface property and photocatalytic activity of the catalysts were investigated. And XRD, TEM, XPS, FTIR and UV–vis diffuse adsorption spectroscopy were used to characterize the obtained powders. The photocatalytic activity of the NTCD was evaluated through the reduction of aqueous Cr (VI) under visible light irradiation (λ > 400 nm). The results demonstrated that the nano-TiO2 particles ranging from 15 to 30 nm in the crystal of anatase are well deposited on the surface of diatomite in the NTCD-500 which calcined at 500 °C for 2 h. Furthermore, the g-C3N4 with the lay thickness of 0.92 nm was attached to the surface of nano-TiO2. The N-doped TiO2 and g-C3N4 doped catalysts could co-enhance response in the visible light region and reduce band gap of NTCD-500 (Eg = 3.07 eV). And the NTCD-500 sample exhibited nearly 100% removal rate within 5 h for photocatalytic reduction of Cr (VI) which was higher activity than P25, crude TiO2@diatomite and g-C3N4@diatomite.

Once released into the environment, engineered nanomaterials can significantly influence the transformation and fate of organic contaminants. To date, the abilities of composite nanomaterials to catalyze environmentally relevant abiotic transformation reactions of organic contaminants are largely unknown. Herein, we investigated the effects of two nanocomposites – consisting of anatase titanium dioxide (TiO2) with different predominantly exposed crystal facets (i.e., {101} or {001} facets) anchored to hydroxylated multi-walled carbon nanotubes (OH-MWCNT) – on the hydrolysis of 1,1,2,2-tetrachloroethane (TeCA), a common groundwater contaminant, at ambient pH (6, 7 and 8). Both OH-MWCNT/TiO2 nanocomposites were more effective in catalyzing the dehydrochlorination of TeCA than the respective component materials (i.e., bare OH-MWCNT and bare TiO2). Moreover, the synergistic effect of the two components was evident, in that the incorporation of OH-MWCNT increased the TeCA adsorption capacity of the nanocomposites, significantly enhancing the catalytic effect of the deprotonated hydroxyl and carboxyl groups on nanocomposite surfaces, which served as the main catalytic sites for TeCA hydrolysis. The findings may have important implications for the understanding of the environmental implications of composite nanomaterials and may shed light on the design of high-performance nanocomposites for enhanced contaminant removal.

Little information is available about effect of particle size and crystal structure of nTiO₂ on their trophic transfer. In this study, 5 nm anatase, 10 nm anatase, 100 nm anatase, 20 nm P25 (80% anatase and 20% rutile), and 25 nm rutile nTiO₂ were selected to investigate the effects of size and crystal structure on the toxicity, bioconcentration, and trophic transfer of nTiO₂ to algae and daphnia. In the exposed daphnids, metabolic pathways affected by nTiO₂ and nTiO₂-exposed algae (nTiO₂-algae) were also explored. The 96 h IC₅₀ values of algae and the 48 h LC₅₀ values of daphnia were 10.3, 18.9, 43.9, 33.6, 65.4 mg/L and 10.5, 13.2, 37.0, 28.4, 60.7 mg/L, respectively, after exposed to nTiO₂-5A, nTiO₂-10A, nTiO₂-100A, nTiO₂-P25, and nTiO₂-25R, respectively. The bioconcentration factors (BCFs) for 0.1, 1, and 10 mg/L nTiO₂ in daphnia ranged from 21,220 L/kg to 145,350 L/kg. The nTiO₂ biomagnification factors (BMFs) of daphnia fed with 1 and 10 mg/L nTiO₂-exposed algae were consistently greater than 1.0 (5.7–122). The results show that the acute toxicity, BCF, and BMF all decreased with increasing size or rutile content of nTiO₂. All types of nTiO₂ were largely accumulated in the daphnia gut and were not completely depurated within 24 h. At the molecular level, 22 Kyoto Encyclopedia of Genes and Genomes (KEGG) metabolic pathways of daphnia were impacted by the nTiO₂ and nTiO₂-algae treatments, including glutathione metabolism, aminoacyl-tRNA biosynthesis, among others. Six and four KEGG metabolic pathways were significantly disturbed in daphnids exposed to nTiO₂ and nTiO₂-algae, respectively, indicating the presence of algae partially alleviated the negative impact of nTiO₂ on metabolism. These findings increase understanding of the impacts of physicochemical properties of nTiO₂ on the food chain from molecular scale to that of the whole organism, and provide new insight into the ecological effect of nanomaterials.