The recent advances in nanotechnology and the corresponding increase in the use of nanomaterials in products in every sector of society have resulted in uncertainties regarding environmental impacts. The objectives of this review are to introduce the key aspects pertaining to nanomaterials in the environment and to discuss what is known concerning their fate, behavior, disposition, and toxicity, with a particular focus on those that make up manufactured nanomaterials. This review critiques existing nanomaterial research in freshwater, marine, and soil environments. It illustrates the paucity of existing research and demonstrates the need for additional research. Environmental scientists are encouraged to base this research on existing studies on colloidal behavior and toxicology. The need for standard reference and testing materials as well as methodology for suspension preparation and testing is also discussed.

Nanomaterials in the environment: Behavior, fate, bioavailability, and effects

Occurrence, behavior and effects of nanoparticles in the environment.

Developments in nanotechnology are leading to a rapid proliferation of new materials that are likely to become a source of engineered nanoparticles (ENPs) to the environment, where their possible ecotoxicological impacts remain unknown. The surface properties of ENPs are of essential importance for their aggregation behavior, and thus for their mobility in aquatic and terrestrial systems and for their interactions with algae, plants and, fungi. Interactions of ENPs with natural organic matter have to be considered as well, as those will alter the ENPs aggregation behavior in surface waters or in soils. Cells of plants, algae, and fungi possess cell walls that constitute a primary site for interaction and a barrier for the entrance of ENPs. Mechanisms allowing ENPs to pass through cell walls and membranes are as yet poorly understood. Inside cells, ENPs might directly provoke alterations of membranes and other cell structures and molecules, as well as protective mechanisms. Indirect effects of ENPs depend on their chemical and physical properties and may include physical restraints (clogging effects), solubilization of toxic ENP compounds, or production of reactive oxygen species. Many questions regarding the bioavailability of ENPs, their uptake by algae, plants, and fungi and the toxicity mechanisms remain to be elucidated.

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Environmental behavior and ecotoxicity of engineered nanoparticles to algae, plants, and fungi

Phytotoxicity of nanoparticles: Inhibition of seed germination and root growth

Nanoparticulate material delivery to plants

The effects of nano-TiO2 (rutile) and non-nano-TiO2 on the germination and growth of naturally aged spinach seeds were studied by measuring the germination rate and the germination and vigor indexes of aged spinach seeds. An increase of these factors was observed at 0.25–4‰ nano-TiO2 treatment. During the growth stage, the plant dry weight was increased, as was the chlorophyll formation, the ribulosebisphosphate carboxylase/oxygenase activity, and the photosynthetic rate. The best results were found at 2.5‰ nano-TiO2. The effects of non-nano-TiO2 are not significant. It is shown that the physiological effects are related to the nanometer-size particles, but the mechanism by which nano-TiO2 improves the growth of spinach seeds still needs further study.

Effect of nano-TiO(2) on strength of naturally aged seeds and growth of spinach.

Previous research showed that nano-TiO2 could significantly promote photosynthesis and greatly improve growth of spinach, but we also speculated that an increase of spinach growth by nano-TiO2 treatment might be closely related to the change of nitrogen metabolism. The effects of nanoanatase TiO2 on the nitrogen metabolism of growing spinach were studied by treating them with nano-anatase TiO2. The results showed that nano-anatase TiO2 treatment could obviously increase the activities of nitrate reductase, glutamate dehydrogenase, glutamine synthase, and glutamic-pyruvic transaminase during the growing stage. Nano-anatase TiO2 treatment could also promote spinach to absorb nitrate, accelerate inorganic nitrogen (such as NO3--N and NH4+-N) to be translated into organic nitrogen (such as protein and chlorophyll), and enhance the fresh weight and dry weights.

Influences of nano-anatase TiO2 on the nitrogen metabolism of growing spinach.

The effects of nano-TiO2 (rutile) on the photochemical reaction of chloroplasts of spinach were studied. The results showed that when spinach was treated with 0.25% nano-TiO2, the Hill reaction, such as the reduction rate of FeCy, and the rate of evolution oxygen of chloroplasts was accelerated and noncyclic photophosphorylation (nc-PSP) activity of chloroplasts was higher than cyclic photophosphorylation (c-PSP) activity, the chloroplast coupling was improved and activities of Mg2+-ATPase and chloroplast coupling factor I (CF1)-ATPase on the thylakoid membranes were obviously activated. It suggested that photosynthesis promoted by nano-TiO2 might be related to activation of photochemical reaction of chloroplasts of spinach.

Effect of nano-TiO2 on photochemical reaction of chloroplasts of spinach.

Having a photocatalyzed characteristic, our previous research had proved that nano-anatase TiO2 is closely related to the photosynthesis of spinach. It could not only improve the light absorbance and the transformation from light energy to electron energy and to active chemical energy but also promote carbon dioxide (CO2) assimilation of spinach. However, the mechanism of carbon reaction promoted by nano-anatase TiO2 remains largely unclear. By electrophoresis and Western blot methods, the results of the experiments proved that Rubisco from the nano-anatase TiO2-treated spinach during the extraction procedure of Rubisco was found to consist of Rubisco and a heavier molecular-mass protein (about 1200 kDa) comprising both Rubisco and Rubisco activase. The Rubisco carboxylase activity was 2.67 times that of Rubisco from the control and it could hydrolyze ATP in the same manner as Rubisco activase. The total sulfhydryl groups and available sulfhydryl groups of the Rubisco were 32-SH and 21-SH per mole of enzyme more than those of the Rubisco purified from the control, respectively. The circular dichroism spectra showed that the secondary structure of Rubisco from the nano-anatase TiO2-treated spinach was very different from Rubisco of the control. It suggested that the mechanism of nano-anatase TiO2 activating Rubisco of spinach was that the complex of Rubsico and Rubisco activase was induced in spinach, which promoted Rubsico carboxylation and increased the rate of photosynthetic carbon reaction.

Mechanism of nano-anatase TiO2 on promoting photosynthetic carbon reaction of spinach: inducing complex of rubisco-rubisco activase.

The improvement of spinach growth is proved to relate to N2 fixation by nano-anatase TiO2 in this study. The results show that all spinach leaves kept green by nano-anatase TiO2 treatment and all old leaves of control turned yellow white under culture with N-deficient solution. And the fresh weight, dry weight, and contents of total nitrogen, % MathType!Translator!2!1!AMS LaTeX.tdl!TeX -- AMS-LaTeX! % MathType!MTEF!2!1!+- % feaaeaart1ev0aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbbjxAHX % garmWu51MyVXgatuuDJXwAK1uy0HwmaeHbfv3ySLgzG0uy0Hgip5wz % aebbnrfifHhDYfgasaacH8qrps0lbbf9q8WrFfeuY-Hhbbf9v8qqaq % Fr0xc9pk0xbba9q8WqFfea0-yr0RYxir-Jbba9q8aq0-yq-He9q8qq % Q8frFve9Fve9Ff0dmeaabaqaciGacaGaaeqabaWaaeWaeaaakeaaca % qGobGaaeisamaaDaaaleaacaaI0aaabaGaey4kaScaaaaa!3AF9! $$ {\text{NH}}^{ + }_{4} $$
 , chlorophyll, and protein of spinach by nano-anatase TiO2 treatment presented obvious enhancement compared with control. Whereas the improvements of yield of spinach were not as good as nano-anatase TiO2 treatment under N-deficient condition, confirming that nano-anatase TiO2 on exposure to sunlight could chemisorb N2 directly or reduce N2 to NH3 in the spinach leaves, transforming into organic nitrogen and improving the growth of spinach. Bulk TiO2 effect, however, was not as significant as nano-anatase TiO2. A possible metabolism of the function of nano-anatase TiO2 reducing N2 to NH3 was discussed.

Chao Liu

Papers

Effect of nano-TiO(2) on strength of naturally aged seeds and growth of spinach.

Influences of nano-anatase TiO2 on the nitrogen metabolism of growing spinach.

Effect of nano-TiO2 on photochemical reaction of chloroplasts of spinach.

Mechanism of nano-anatase TiO2 on promoting photosynthetic carbon reaction of spinach: inducing complex of rubisco-rubisco activase.

The improvement of spinach growth by nano-anatase TiO2 treatment is related to nitrogen photoreduction.