Titanium dioxide nanoparticles (TiO2 NPs) have been widely used in agriculture, which increased the risk to soilplant systems. Studies have demonstrated that TiO2 NPs can induce phytotoxicity. However, the toxicity mechanisms, particularly under the stress of TiO2 NPs with different crystalline forms, remain inadequately reported. In this study, we combined transcriptomics and metabolomics to analyze the toxicity mechanisms in rice (Oryza sativa L.) under the stress of anatase (AT) or rutile (RT) TiO2 NPs (50 mg/kg, 40 days). The length (decreased by 1.1-fold, p = 0.021) and malondialdehyde concentration (decreased by 1.4-fold, p = 0.0027) of rice shoots was significantly reduced after AT exposure, while no significant changes were observed following RT exposure. Antioxidant enzyme activities were significantly altered both in the AT and RT groups, indicating TiO2 NPs induced rice oxidative damage (with changes of 1.1 to 1.4-fold, p < 0.05). Additionally, compared to the control, AT exposure altered 3247 differentially expressed genes (DEGs) and 56 significantly differentially metabolites in rice (collectively involved in pyrimidine metabolism, TCA cycle, fatty acid metabolism, and amino acid metabolism). After RT exposure, 2814 DEGs and 55 significantly differentially metabolites were identified, which were collectively involved in fatty acid metabolism and amino acid metabolism. Our results indicated that AT exposure led to more pronounced changes in biological responses related to oxidative stress and had more negative effects on rice growth compared to RT exposure. These findings provide new insights into the phytotoxic mechanisms of TiO2 NPs with different crystalline forms. Based on the observed adverse effects, the study emphasizes that any form of TiO2 NPs should be used with caution in rice ecosystems. This study is the first to demonstrate that AT is more toxic than RT in paddy ecosystems, providing crucial insights into the differential impacts and toxic mechanisms of TiO2 NPs with different crystalline forms. These findings suggest prioritizing the use of RT when TiO2 NPs are necessary in agricultural development to minimize toxicity risks.

Titanium dioxide (TiO2) is one of the most studied oxides in photocatalysis, due to its electronic structure and its wide variety of applications, such as gas sensors and biomaterials, and especially in methane-reforming catalysis. Titanium dioxide and olivine have been detected both on Mars and our Moon. It has been postulated that on Mars photocatalytic processes may be relevant for atmospheric methane fluctuation, radicals and perchlorate pro-ductions etc. However, to date no investigation has been devoted to modelling the properties of TiO2 adsorbed on olivine surface. The goal of this study is to investigate at atomic level with electronic structure calculations based on the Density Functional Theory (DFT), the atomic interactions that take place during the adsorption processes for formation of a TiO regolith. These models are formed with different titanium oxide films adsorbed on olivine (forsterite) surface, one of the most common minerals in Universe, Earth, Mars, cometary and interstellar dust. We propose three regolith models to simulate the principal phases of titanium oxide (TiO, Ti2O3 and TiO2). The models show different adsorption processes Le. physisorption and chemisorption. Our results suggest that the TiO is the most reactive phase and produces a strong exothermic effect. Besides, we have detailed, from a theoretical point of view, the effect that has the adsorption process in the electronic properties such as electronic density of states (DOS) and oxide reduction process (redox). This theoretical study can be important to understand the formation of new materials that can be used as support in the catalytic processes that occur in the Earth, Mars and Moon. Also, it may be important to interpret the present day photochemistry and interaction of regolith and airborne aerosols in the atmosphere on Mars or to define possible catalytic reactions of the volatiles captured on the Moon regolith.