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.

Bisphenol A (BPA) is a widely concerned endocrine disrupting chemical and hard to be removed through conventional wastewater treatment processes. In this study, we developed a TiO2 decorated titanate nanotubes composite (TiO2/TNTs) and used for photocatalytic degradation of BPA. TEM and XRD analysis show that the TiO2/TNTs is a nano-composite of anatase and titanate, with anatase acting as the primary photocatalytic site and titanate as the skeleton. TiO2/TNTs exhibited excellent photocatalytic reactivity and its easy-settling property leaded to good reusability. After 5 reuse cycles, TiO2/TNTs also could photo-degrade 91.2% of BPA with a high rate constant (k1) of 0.039 min⁻¹, which was much better than TiO2 and TNTs. Higher pH facilitated photocatalysis due to more reactive oxygen species produced and less material aggregation. The presence of NaCl and CaCl2 showed negligible effects on BPA degradation, but NaHCO3 caused an inhibition effect resulting from consumption of ·OH. Humic acid inhibited degradation mainly due to blockage of the active sites of TiO2/TNTs. Degradation pathway was well interpreted through theoretical calculation. Hydroxyl radical played the dominate role in BPA photodegradation, and the atoms of BPA with high Fukui index based on density-functional theory (DFT) calculation are the radical easy-attacking (f⁰) sites. Considering the good photocatalytic reactivity, reusability, stability and settle property, TiO2/TNTs promises to be an efficient alternative for removal of organic compounds from wastewaters.

The mechanism of enhanced accumulation of organic contaminants in crops with engineered nanomaterials (ENMs) were investigated by co-exposure of crops (Ipomoea aquatica Forsk (Swamp morning-glory), Cucumis sativus L. (cucumber), Zea mays L. (corn), Spinacia oleracea L. (spinach) and Cucurbita moschata (pumpkin))to a range of chemicals (polycyclic aromatic hydrocarbons (PAHs), organochlorine pesticides (OCPs) and polybrominated diphenyl ether (PBDE)) and ENMs (TiO2, Ag, Al2O3, graphene, carbon nanotubes (CNTs)) in soil. Induced by 50 mg kg−1 graphene co-exposure, the increase range of BDE-209, BaP, p,p′-DDE, HCB, PYR, FLU, ANT, and PHEN in the plants were increased in the range of 7.51–36.42, 5.69–32.77, 7.09–59.43, 11.61–66.73, 4.58–57.71, 5.79–109.07, 12.85–109.76, and15.57–127.75 ng g−1, respectively. The contaminants in ENMs-spiked and control soils were separated into bioavailable, bound and residual fractions using a sequential ultrasonic extraction procedure (SUEP) to investigate the mechanism of the enhanced accumulation. The bioavailable fraction in spiked soils showed no significant difference (p > 0.05) from that in the control, while the bound fraction increased in equal proportion (p > 0.05) to the reduction in the residual fraction. These results implied that ENMs can competitively adsorbed the bound of organic contaminants from soil and co-transferred into crops, followed by a portion of the residual fraction transferred to the bound fraction to maintain the balance of different fractions in soils. The mass balance was all higher than 98.5%, indicating the portion of degraded contaminants was less than 1.5%. These findings could expand our knowledge about the organic contaminants accumulation enhancement in crops with ENMs.

Nanosized particles (NPs), such as TiO₂, Silver, graphene NPs, nanoscale zero-valent iron, carbon nanotubes, etc., are increasingly used in industrial processes, and releases at production plants and from landfills are likely scenarios for the next years. As a consequence, appropriate procedures and tools to quantify the risks for human health associated to these releases are needed.The tiered approach of the standard ASTM procedure (ASTM-E2081-00) is today the most applied for human health risk assessment at sites contaminated by chemical substances, but it cannot be directly applied to nanoparticles: NP transport along migration pathways follows mechanisms significantly different from those of chemicals; moreover, also toxicity indicators (namely, reference dose and slope factor) are NP-specific. In this work a risk assessment approach modified for NPs is proposed, with a specific application at Tier 2 to migration in groundwater. The standard ASTM equations are modified to include NP-specific transport mechanisms. NPs in natural environments are typically characterized by a heterogeneous set of NPs having different size, shape, coating, etc. (all properties having a significant impact on both mobility and toxicity). To take into account this heterogeneity, the proposed approach divides the NP population into classes, each having specific transport and toxicity properties, and simulates them as independent species. The approach is finally applied to a test case simulating the release of heterogeneous Silver NPs from a landfill. The results show that taking into account the size-dependent mobility of the particles provides a more accurate result compared to the direct application of the standard ASTM procedure. In particular, the latter tends to underestimate the overall toxic risk associated to the nP release.

Gut microbiota is of critical relevance to host health. However, toxicological understanding of environmental pollutants on gut microbiota is limited, not to mention their combined effects. In the present study, adult zebrafish (Danio rerio) were exposed to titanium dioxide nanoparticles (nano-TiO₂; 100 μg/L), bisphenol A (BPA; 0, 2, and 20 μg/L) or their binary mixtures for three months. Sequencing of 16S rRNA amplicons found that nano-TiO₂ and BPA coexposure shifted the intestinal microbial community, interacting in an antagonistic manner when the BPA concentration was low but in a synergistic manner at a higher BPA concentration. Sex- and concentration-dependent responses to the coexposure regime were also observed for zebrafish growth and intestinal health (e.g. neurotransmission, epithelial barrier permeability, inflammation, and oxidative stress). Correlation analysis showed that oxidative stress after nano-TiO₂ and BPA coexposure was tightly associated with the imbalanced ratio of pathogenic Lawsonia and normal metabolic Hyphomicrobium, where higher abundance of Lawsonia but lower abundance of Hyphomicrobium were induced concurrently. A positive relationship was observed between zebrafish body weight and the abundance of Bacteroides in the gut, which was also closely associated with the genera of Anaerococcus, Finegoldia, and Peptoniphilus. This study revealed, for the first time, the combined effects of nano-TiO₂ and BPA coexposure on the dynamics of the gut microbiome, which proved to have toxicological implications for zebrafish host health.