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.

In predicting palm oil mill effluent (POME) degradation efficiency, previous developed quadratic model quantitatively evaluated the effects of O2 flowrate, TiO2 loadings and initial concentration of POME in labscale photocatalytic system, which however suffered from low generalization due to the overfitting behaviour. Evidently, high RMSE (131.61) and low R₂ (−630.49) obtained indicates its insufficiency in describing POME degradation at unseen factor ranges, hence verified the fact of poor generalization. To overcome this issue, several models were developed via machine learning-assisted techniques, namely Gaussian Process Regression (GPR), Linear Regression (LR), Decision Tree (DT), Supported Vector Machine (SVM) and Regression Tree Ensemble (RTE), subsequently being assessed systematically. To achieve high generalization, all models were subjected to ‘train-all-test-all’ strategy, 5-fold and 10-fold cross validation. Specifically, GPR model was furnished with high accuracy in ‘train-all-test-all’ strategy, judging from its low RMSE (1.0394) and high R₂ (0.9962), which however menaced by the risk of overfitting. In contrast, despite relatively poorer RMSE and R₂ (1.7964 and 0.9886) obtained in 5-fold cross validation, GPR model was rendered with highest generalization, while sufficiently preserving its accuracy in development process. Besides, SVM and RTE models were also demonstrated promising R₂ (0.9372 and 0.9208), which however shadowed by their high RMSEs (4.2174 and 4.7366). Furthermore, the extraordinary generalization of GPR model was coincidentally verified in 10-fold cross validation. The lowest RMSE (2.1624) and highest R₂ (0.9835) obtained with feature number of 36 asserted its sufficiency in both generalization and accuracy prospect. Other models were all rendered with slight lower R₂ (> 0.9), plausibly due to the higher RMSE (> 4.0). According to GPR model, optimized POME degradation (52.52%) can be obtained at 70 mL/min of O₂, 70.0 g/L of TiO₂ and 250 ppm of POME concentration, with only ∼3% error as compared to the actual data.

As an important part of extracellular secondary metabolites, extracellular polymeric substances (EPS) can play a significant role in protecting cells from the threat of exogenous substances, including nanoparticles (NPs). However, the regulation mechanisms of EPS secretion under NPs exposure remain largely unknown. This study investigated the signaling pathways and molecular responses related to EPS secretion of algae (Chlorella pyrenoidosa) upon the exposures to anatase and rutile TiO₂ NPs (nTiO₂-A and nTiO₂-R, respectively) at two similar toxic (20% and 50% of algal growth inhibition) concentrations. The results showed that EPS responded to nTiO₂ stress via excess secretion and compositional variation, and nTiO₂-A induced more EPS secretion than nTiO₂-R at similar toxicity concentrations. The up-regulation of the Ca²⁺ signaling pathway might play a greater role in promoting EPS secretion under nTiO₂-R exposure compared with nTiO₂-A exposure, while the significantly increased intracellular ROS could mainly account for the increased EPS secretion under nTiO₂-A exposure. The up-regulated genes related to biological synthesis and protein metabolism and the enhanced biosynthetic metabolism might be the direct causes of the increased EPS secretion. The increased ROS could have a greater effect on the amino acid metabolism and related genes upon the exposure to nTiO₂-A than nTiO₂-R to induce more EPS secretion. More serious membrane damage caused by nTiO₂-R than nTiO₂-A would affect the intracellular inositol phospholipid metabolism more severely, while the inositol phospholipid pathway and Ca²⁺ signaling pathway might agree and communicate with each other inherently to regulate EPS secretion upon nTiO₂-R exposure. The findings address the regulation mechanisms of algal EPS secretion under nTiO₂ exposure and provide new insights into algal bio-responses to nTiO₂ exposure.

With increasing release of nanoparticles (NPs) into the environment, soil organisms likely suffer from high dose and long duration of NPs contamination, while the effect of NPs across multiple generations in soil is rarely studied. Herein, we investigated how multigenerational exposure to different crystal forms (anatase, rutile, and their mixture) of TiO₂ NPs (nTiO₂) affected the survival, behavior, physiological and biochemical traits, and lifespan of nematodes (C. elegans) in a paddy soil. The soil property changed very slightly after being spiked with nTiO₂, and the toxicities of three nTiO₂ forms were largely comparable. The nTiO₂ exposure adversely influenced the survival and locomotion of nematodes, and increased intracellular reactive oxygen species (ROS) generation. Interestingly, the toxic effect gradually attenuated and the lifespan of survived nematodes increased from the P0 to F3 generation, which was ascribed to the survivor selection and stimulatory effect. The lethal effect and the increased oxidative stress may continuously screen out offspring possessing stronger anti-stress capabilities. Moreover, key genes (daf-2, age-1, and skn-1) in the insulin/IGF-like signaling (IIS) pathway actively responded to the nTiO₂ exposure, which further optimized the selective expression of downstream genes, increased the antioxidant enzyme activities and antioxidant contents, and thereby increased the stress resistance and longevity of survived nematodes across successive generations. Our findings highlight the crucial role of bio-responses in the progressively decreased toxicity of nTiO₂, and add new knowledge on the long-term impact of soil nTiO₂ contamination.

Natural media such as soil and sediment contain mineralogical and organic components with distinct chemical, surface, and electrostatic properties. To better understand the role of various soil and sediment components on particle transport, columns were packed with quartz sand and natural sediment with added Fe oxyhydroxide coating, illite clay, and peat moss to investigate how these added components influence nTiO₂ retention and transport in geochemically heterogeneous medium. Results showed that nTiO₂ transport was low at pH 5, attributable to the electrostatic attraction between positively-charged nTiO₂ and negatively-charged medium. While illite did not notably affect nTiO₂ transport at pH 5, Fe oxyhydroxide coating increased nTiO₂ transport due to electrostatic repulsion between Fe oxyhydroxide and nTiO₂. Peat moss also increased nTiO₂ transport at pH 5, attributable to the increased DOC concentration, which resulted in higher DOC adsorption to nTiO₂ and intensified electrostatic repulsion between nTiO₂ and the medium. At pH 9, nTiO₂ transport was high due to the electrostatic repulsion between negatively-charged nTiO₂ and medium surfaces. Fe oxyhydroxide coating at pH 9 slightly delayed nTiO₂ transport due to electrostatic attraction, while illite clay and peat moss substantially inhibited nTiO₂ transport via straining/entrapment or electrostatic attraction. Overall, this study demonstrated that pH has a considerable effect on how minerals and organic components of a medium influence nTiO₂ transport. At low pH, electrostatic attraction was the dominant mechanism, therefore, nTiO₂ mobility was low regardless of the differences in mineralogical and organic components. Conversely, nTiO₂ mobility was high at high pH and nTiO₂ retention was dominated by straining/entrapment and sensitive to the mineralogical and organic composition of the medium.

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.

Particulate matter (PM) can strongly affect redox biochemistry and therefore induce the response of the immune system and aggravate the course of autoimmune diseases. Nanoparticles containing transition metal compounds possessing semiconductor properties (TiO2, ZnO) may act as photocatalysts and accelerate the generation of reactive oxygen species (ROS) and reactive nitrogen species (RNS). In this study, the NIST standard reference material, SRM 1648a, has been analyzed in terms of this consideration. Organic compounds present in SRM 1648a were removed by cold oxygen plasma treatment. Samples of SRM 1648a with removed organic content (<2% of organic carbon, <1% of nitrogen) were obtained within 2 h of this treatment. The treatment did not affect the morphology of the powder. The reference material and PM2.5 collected in Kraków are composed of smaller particles and nanoparticles forming aggregates. The efficiency of (photo)generation of hydroxyl radicals and singlet oxygen was compared for original and organics-free samples. The analyzed samples showed the highest activity towards ROS generation when exposed to UV-vis-NIR light, moderate under UV irradiation, and the lowest in dark. Data collected in the present study suggest that the organic fraction is mostly responsible for singlet oxygen generation, as almost twice higher efficiency of 1O2 generation was observed for the original NIST sample compared to the material without the organic fraction. However, particulate matter collected in Kraków was found to have a five times higher activity in singlet oxygen generation (compared for original NIST and Kraków dust samples).

A comprehensive study of the removal of selected biologically active compounds (pharmaceuticals and pesticides) from different water types was conducted using bare TiO₂ nanoparticles and TiO₂/polyaniline (TP-50, TP-100, and TP-150) nanocomposite powders. In order to investigate how molecular structure of the substrate influences the rate of its removal, we compared degradation efficiency of the initial substrates and degree of mineralization for the active components of pharmaceuticals (propranolol, and amitriptyline) and pesticides (sulcotrione, and clomazone) in double distilled (DDW) and environmental waters. The results indicate that the efficiency of photocatalytic degradation of propranolol and amitriptyline was higher in environmental waters: rivers (Danube, Tisa, and Begej) and lakes (Moharač, and Sot) in comparison with DDW. On the contrary, degradation efficacy of sulcotrione and clomazone was lower in environmental waters. Further, of the all catalysts applied, bare TiO₂ and TP-100 were found to be most effective in the mineralization of propranolol and amitriptyline, respectively, while TP-150 appeared to be the most efficient in terms of sulcotrione and clomazone mineralization. Also, there was no significant toxicity observed after the irradiation of pharmaceuticals or pesticides solutions using appropriate catalysts on rat hepatoma (H-4-II-E), mouse neuroblastoma (Neuro-2a), human colon adenocarcinoma (HT-29), and human fetal lung (MRC-5) cell lines. Subsequently, detection and identification of the formed intermediates in the case of sulcotrione photocatalytic degradation using bare TiO₂ and TP-150 showed slightly different pathways of degradation. Furthermore, tentative pathways of sulcotrione photocatalytic degradation were proposed and discussed.

The effect of titanium dioxide nanoparticles (nano-TiO2) on the bioaccumulation and biotransformation of arsenic (As) remains largely unknown. In this study, we exposed two freshwater algae (Microcystis aeruginosa and Scenedesmus obliquus) to inorganic As (arsenite and arsenate) with the aim of increasing our understanding on As bioaccumulation and methylation in the presence of nano-TiO2. Direct evidence from transmission electron microscope (TEM) images show that nano-TiO2 (anatase) entered exposed algae. Thus, nano-TiO2 as carriers boosted As accumulation and methylation in these two algae species, which varied between inorganic As speciation and algae species. Specifically, nano-TiO2 could markedly enhance arsenate (As(V)) accumulation in M. aeruginosa and arsenite (As(III)) accumulation in S. obliquus. Similarly, we found evidence of higher As methylation activity in the M. aeruginosa of As(III) 2 mg L−1 nano-TiO2 treatment. Although this was also true for the S. obliquus (As(V)) treatment, this species exhibited higher As methylation compared to M. aeruginosa, being more sensitive to As associated with nano-TiO2 compared to M. aeruginosa. Due to changes in pH levels inside these exposed algae, As dissociation from nano-TiO2 inside algal cells enhanced As methylation. Accordingly, the potential influence of nanoparticles on the bioaccumulation and biotransformation of their co-contaminants deserves more attention.