Interactions between engineered nanoparticles (ENPs) and plants: phytotoxicity, uptake and accumulation

To the Editor — Nitrogen, which is a key nutrient source for food, biomass, and fibre production in agriculture, is by far the most important element in fertilizers when judged in terms of the energy required for its synthesis, tonnage used and monetary value. However, compared with amounts of nitrogen applied to soil, the nitrogen use efficiency (NUE) by crops is very low. Between 50 and 70% of the nitrogen applied using conventional fertilizers — plant nutrient formulations with dimensions greater than 100 nm — is lost owing to leaching in the form of water soluble nitrates, emission of gaseous ammonia and nitrogen oxides, and long-term incorporation of mineral nitrogen into soil organic matter by soil microorganisms1. Numerous attempts to increase the NUE have so far met with little success, and the time may have come to apply nanotechnology to solve some of these problems. Carbon nanotubes were recently shown to penetrate tomato seeds2, and zinc oxide nanoparticles were shown to enter the root tissue of ryegrass3 (Fig. 1). This suggests that new nutrient delivery systems that exploit the nanoscale porous domains on plant surfaces can be developed. The potential use of nanotechnology to improve fertilizer formulations, however, may have been hindered by reduced research funding and the lack of clear regulations and innovation policies. Current patent literature shows that the use of nanotechnology in fertilizer development remains relatively low (about 100 patents and patent applications between 1998 and 2008) compared with pharmaceuticals (more than 6,000 patents and patent applications over the same period)4. A nanofertilizer refers to a product that delivers nutrients to crops in one of three ways. The nutrient can be encapsulated inside nanomaterials such as nanotubes or nanoporous materials, coated with a thin protective polymer film, or delivered as particles or emulsions of nanoscale dimensions. Owing to a high surface area to volume ratio, the effectiveness of nanofertilizers may surpass the most innovative polymer-coated conventional fertilizers, which have seen little improvement in the past ten years. Ideally, nanotechnology could provide devices and mechanisms to synchronize the release of nitrogen (from fertilizers) with its uptake by crops; the nanofertilizers should release the nutrients on-demand while preventing them from prematurely converting into chemical/gaseous forms that cannot be absorbed by plants. This can be achieved by preventing nutrients from interacting with soil, water and microorganisms, and releasing nutrients only when they can be directly internalized by the plant. Examples of these nanostrategies are beginning to emerge. Zinc–aluminiumlayered double-hydroxide nanocomposites have been used for the controlled release of chemical compounds that regulate plant growth5. Improved yields have been claimed for fertilizers that are incorporated into cochleate nanotubes (rolled-up lipid bilayer sheets)6. The release of nitrogen by urea hydrolysis has been controlled through the insertion of urease enzymes into nanoporous silica7. Although these approaches are promising, they lack mechanisms that can recognize and respond to the needs of the plant and changes in nitrogen levels in the soil. The development of functional nanoscale films8 and devices has the potential to produce significant gains in the NUE and crop production. In addition to increasing the NUE, nanotechnology might be able to improve the performance of fertilizers in other ways. For example, owing to its photocatalytic property, nanosize titanium dioxide has been incorporated into fertilizers as a bactericidal additive. Moreover, titanium dioxide may also lead to improved crop yield through the photoreduction of nitrogen gas9. Furthermore, nanosilica particles absorbed by roots have been shown to form films at the cell walls, which can enhance the plant’s resistance to stress and lead to improved yields10. Clearly, there is an opportunity for nanotechnology to have a profound impact on energy, the economy and the environment, by improving fertilizer products. New prospects for integrating nanotechnologies into fertilizers should be explored, cognizant of any potential risk to the environment or to human health. With targeted efforts by governments and academics in developing such enabled agriproducts, we believe that nanotechnology will be transformative in this field. ❐

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Nanotechnology in fertilizers

Phytotoxicity is an important consideration to understand the potential environmental impacts of manufactured nanomaterials. Here, we report on the effects of four metal oxide nanoparticles, aluminum oxide (nAl(2)O(3)), silicon dioxide (nSiO(2)), magnetite (nFe(3)O(4)), and zinc oxide (nZnO), on the development of Arabidopsis thaliana (Mouse-ear cress). Three toxicity indicators (seed germination, root elongation, and number of leaves) were quantified following exposure to each nanoparticle at three concentrations: 400, 2,000, and 4,000 mg/L. Among these particles, nZnO was most phytotoxic, followed by nFe(3)O(4), nSiO(2), and nAl(2)O(3), which was not toxic. Consequently, nZnO was further studied to discern the importance of particle size and zinc dissolution as toxicity determinants. Soluble zinc concentrations in nanoparticle suspensions were 33-fold lower than the minimum inhibitory concentration of dissolved zinc salt (ZnCl(2)), indicating that zinc dissolution could not solely account for the observed toxicity. Inhibition of seed germination by ZnO depended on particle size, with nanoparticles exerting higher toxicity than larger (micron-sized) particles at equivalent concentrations. Overall, this study shows that direct exposure to nanoparticles significantly contributed to phytotoxicity and underscores the need for eco-responsible disposal of wastes and sludge containing metal oxide nanoparticles.

https://setac.onlinelibrary.wiley.com/doi/pdf/10.1002/etc.58

Developmental phytotoxicity of metal oxide nanoparticles to Arabidopsis thaliana

Role of nano-SiO2 in germination of tomato (Lycopersicum esculentum seeds Mill.).

Elemental silicon (Si), after oxygen, is the second most abundant element in the earth’s crust, which is mainly composed of silicates. Si is not considered essential for plant growth and development, however increasing evidence in the literature shows that this metalloid is beneficial to plants, especially under stress conditions. Indeed Si alleviates the toxic effects caused by abiotic stresses, e.g. salt stress, drought, heavy metals, to name a few. Biogenic silica is also a deterrent against herbivores. Additionally, Si ameliorates the vigour of plants and improves their resistance to exogenous stresses. The protective role of Si was initially attributed to a physical barrier fortifying the cell wall (e.g. against fungal hyphae penetration), however several studies have shown that the action of this element on plants is far more complex, as it involves a cross-talk with the cell interior and an effect on plant metabolism. In this study the beneficial role of Si on plants will be discussed, by reviewing the available data in the literature. Emphasis will be given to the protective role of Si during (a)biotic stresses and in this context both priming and the effects of Si on endogenous phytohormones will be discussed. A whole section will be devoted to the use of silica (SiO2) nanoparticles, in the light of the interest that nanotechnology has for agriculture. The paper also discusses the potential technological aspects linked to the use of Si in agriculture and to modify/improve the physical parameters of plant fibers. The study indeed provides perspectives on

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Silicon and Plants: Current Knowledge and Technological Perspectives.

The roots of 200 one-year-old Changbai Larch (Larix olgensis) seedlings were soaked for 6 hours at the TMS concentrations of 2000, 1000, 500, 250, 125, and 62 μL·L−1 Mean seedling height, root collar diameter, main root length and number of lateral roots were measured every 15 days during growing season from May 30 to Oct 20 Experimental results showed that TMS treatments greatly promoted seedling growth and improved seedling quality The treatment by 500 μL·L−1 TMS produced the best result, for which the mean height, root collar diameter, main root length, and the number of lateral roots of seedlings were increased by 425%, 307%, 140%, and 316%, respectively, compared to that of the control seedlings As to seedling quality, grade-I seedling and grade-II seedlings were fifty-fifty, and no grade-III seedlings was found The treatment by 500 μL·L−1 TMS resulted in the highest chlorophyll concentration

Yu Min

Papers

Effect of TMS (nanostructured silicon dioxide) on growth of Changbai larch seedlings