Lignin-based nano-enabled agriculture: A mini-review.

Nowadays sustainable nanotechnological strategies to improve the efficiency of conventional agricultural practices are of utmost importance. As a matter of fact, the increasing use of productive factors in response to the growing food demand plays an important role in determining the environmental impact of agriculture. In this respect, low-efficiency conventional practices are becoming obsolete. On the other hand, the exploitation of nanoscaled systems for the controlled delivery of fertilizers, pesticides and herbicides shows great potential towards the development of sustainable, efficient and resilient agricultural processes, while promoting food security. In this context, lignin - especially in the form of its nanostructures - can play an important role as sustainable biomaterial for nano-enabled agricultural applications. In this review, we present and discuss the current advancements in the preparation of lignin nanoparticles for the controlled release of pesticides, herbicides, and fertilizers, as well as the latest findings in terms of plant response to their application. Special attention has been paid to the state-of-the-art literature concerning the release performance of these lignin-based nanomaterials, whose efficiency is compared with the conventional approaches. Finally, the major challenges and the future scenarios of lignin-based nano-enabled agriculture are considered.

Calcium Phosphate Particles Coated with Humic Substances: A Potential Plant Biostimulant from Circular Economy.

Nowadays, the use of biostimulants to reduce agrochemical input is a major trend in agriculture. In this work, we report on calcium phosphate particles (CaP) recovered from the circular economy, combined with natural humic substances (HSs), to produce a plant biostimulant. CaPs were obtained by the thermal treatment of Salmo salar bones and were subsequently functionalized with HSs by soaking in a HS water solution. The obtained materials were characterized, showing that the functionalization with HS did not sort any effect on the bulk physicochemical properties of CaP, with the exception of the surface charge that was found to get more negative. Finally, the effect of the materials on nutrient uptake and translocation in the early stages of development (up to 20 days) of two model species of interest for horticulture, Valerianella locusta and Diplotaxis tenuifolia, was assessed. Both species exhibited a similar tendency to accumulate Ca and P in hypogeal tissues, but showed different reactions to the treatments in terms of translocation to the leaves. CaP and CaP-HS treatments lead to an increase of P accumulation in the leaves of D. tenuifolia, while the treatment with HS was found to increase only the concentration of Ca in V. locusta leaves. A low biostimulating effect on both plants' growth was observed, and was mainly scribed to the low concentration of HS in the tested materials. In the end, the obtained material showed promising results in virtue of its potential to elicit phosphorous uptake and foliar translocation by plants.

Influence of Cerium Oxide Nanoparticles on Two Terrestrial Wild Plant Species.

Most current studies on the relationships between plans and engineered nanomaterials (ENMs) are focused on food crops, while the effects on spontaneous plants have been neglected so far. However, from an ecological perspective, the ENMs impacts on the wild plants could have dire consequences on food webs and ecosystem services. Therefore, they should not be considered less critical. A pot trial was carried out in greenhouse conditions to evaluate the growth of Holcus lanatus L. (monocot) and Diplotaxis tenuifolia L. DC. (dicot) exposed to cerium oxide nanoparticles (nCeO2). Plants were grown for their entire cycle in a substrate amended with 200 mg kg-1nCeO2 having the size of 25 nm and 50 nm, respectively. nCeO2 were taken up by plant roots and then translocated towards leaf tissues of both species. However, the mean size of nCeO2 found in the roots of the species was different. In D. tenuifolia, there was evidence of more significant particle aggregation compared to H. lanatus. Further, biomass variables (dry weight of plant fractions and leaf area) showed that plant species responded differently to the treatments. In the experimental conditions, there were recorded stimulating effects on plant growth. However, nutritional imbalances for macro and micronutrients were observed, as well.

Single and Repeated Applications of Cerium Oxide Nanoparticles Differently Affect the Growth and Biomass Accumulation of Silene flos-cuculi L. (Caryophyllaceae).

Cerium oxide nanoparticles (nCeO2) have a wide variety of applications in industry. Models demonstrated that nCeO2 can reach environmental compartments. Studies regarding the relationships between plants and nCeO2 considered only crop species, whereas a relevant knowledge gap exists regarding wild plant species. Specimens of Silene flos-cuculi (Caryophyllaceae) were grown in greenhouse conditions in a substrate amended with a single dose (D1) and two and three doses (D2 and D3) of 20 mg kg-1 and 200 mg kg-1 nCeO2 suspensions, respectively. sp-ICP-MS and ICP-MS data demonstrated that nCeO2 was taken up by plant roots and translocated towards aerial plant fractions. Biometric variables showed that plants responded negatively to the treatments with a shortage in biomass of roots and stems. Although not at relevant concentrations, Ce was accumulated mainly in roots and plant leaves.

Germination and Early Development of Three Spontaneous Plant Species Exposed to Nanoceria (nCeO2) with Different Concentrations and Particle Sizes.

This study aimed to provide insight regarding the influence of Ce oxide nanoparticles (nCeO2) with different concentrations and two different particle sizes on the germination and root elongation in seedlings of spontaneous terrestrial species. In a bench-scale experiment, seeds of the monocot, Holcus lanatus and dicots Lychnis-flos-cuculi and Diplotaxis tenuifolia were treated with solutions containing nCeO2 25 nm and 50 nm in the range 0-2000 mg Ce L-1. The results show that nCeO2 enters within the plant tissues. Even at high concentration, nCeO2 have positive effects on seed germination and the development of the seedling roots. This study further demonstrated that the particle size had no influence on the germination of L. flos-cuculi, while in H. lanatus and D. tenuifolia, the germination percentage was slightly higher (+10%) for seeds treated with nCeO2 25 nm with respect to 50 nm. In summary, the results indicated that nCeO2 was taken up by germinating seeds, but even at the highest concentrations, they did not have negative effects on plant seedlings. The influence of the different sizes of nCeO2 on germination and root development was not very strong. It is likely that particle agglomeration and ion dissolution influenced the observed effects.

Effects of Cerium and Titanium Oxide Nanoparticles in Soil on the Nutrient Composition of Barley (Hordeum vulgare L.) Kernels.

The implications of metal nanoparticles (MeNPs) are still unknown for many food crops. The purpose of this study was to evaluate the effects of cerium oxide (nCeO2) and titanium oxide (nTiO2) nanoparticles in soil at 0, 500 and 1000 mg·kg(-1) on the nutritional parameters of barley (Hordeum vulgare L.) kernels. Mineral nutrients, amylose, ß-glucans, amino acid and crude protein (CP) concentrations were measured in kernels. Whole flour samples were analyzed by ICP-AES/MS, HPLC and Elemental CHNS Analyzer. Results showed that Ce and Ti accumulation under MeNPs treatments did not differ from the control treatment. However, nCeO2 and nTiO2 had an impact on composition and nutritional quality of barley kernels in contrasting ways. Both MeNPs left ß-glucans unaffected but reduced amylose content by approximately 21%. Most amino acids and CP increased. Among amino acids, lysine followed by proline saw the largest increase (51% and 37%, respectively). Potassium and S were both negatively impacted by MeNPs, while B was only affected by 500 mg nCeO2·kg(-1). On the contrary Zn and Mn concentrations were improved by 500 mg nTiO2·kg(-1), and Ca by both nTiO2 treatments. Generally, our findings demonstrated that kernels are negatively affected by nCeO2 while nTiO2 can potentially have beneficial effects. However, both MeNPs have the potential to negatively impact malt and feed production.

Changes in Physiological and Agronomical Parameters of Barley (Hordeum vulgare) Exposed to Cerium and Titanium Dioxide Nanoparticles.

The aims of our experiment were to evaluate the uptake and translocation of cerium and titanium oxide nanoparticles and to verify their effects on the growth cycle of barley (Hordeum vulgare L.). Barley plants were grown to physiological maturity in soil enriched with either 0, 500 or 1000 mg · kg(-1) cerium oxide nanoparticles (nCeO2) or titanium oxide nanoparticles (nTiO2) and their combination. The growth cycle of nCeO2 and nTiO2 treated plants was about 10 days longer than the controls. In nCeO2 treated plants the number of tillers, leaf area and the number of spikes per plant were reduced respectively by 35.5%, 28.3% and 30% (p ≤ 0.05). nTiO2 stimulated plant growth and compensated for the adverse effects of nCeO2. Concentrations of Ce and Ti in aboveground plant fractions were minute. The fate of nanomaterials within the plant tissues was different. Crystalline nTiO2 aggregates were detected within the leaf tissues of barley, whereas nCeO2 was not present in the form of nanoclusters.

Toward the Standardization of Biochar Analysis: The COST Action TD1107 Interlaboratory Comparison.

Biochar produced by pyrolysis of organic residues is increasingly used for soil amendment and many other applications. However, analytical methods for its physical and chemical characterization are yet far from being specifically adapted, optimized, and standardized. Therefore, COST Action TD1107 conducted an interlaboratory comparison in which 22 laboratories from 12 countries analyzed three different types of biochar for 38 physical-chemical parameters (macro- and microelements, heavy metals, polycyclic aromatic hydrocarbons, pH, electrical conductivity, and specific surface area) with their preferential methods. The data were evaluated in detail using professional interlaboratory testing software. Whereas intralaboratory repeatability was generally good or at least acceptable, interlaboratory reproducibility was mostly not (20% < mean reproducibility standard deviation < 460%). This paper contributes to better comparability of biochar data published already and provides recommendations to improve and harmonize specific methods for biochar analysis in the future.

Variation in Heavy Metal Accumulation and Genetic Diversity at a Regional Scale Among Metallicolous and Non-Metallicolous Populations of the Facultative Metallophyte Biscutella laevigata subsp. laevigata.

Biscutella laevigata is a facultative metallophyte, with populations on non-metalliferous and metalliferous soils. Some of its metallicolous populations have been shown to hyperaccumulate thallium or lead in nature. Only Tl hyperaccumulation has been experimentally confirmed. We aimed to compare the patterns of metal (hyper)accumulation and genetic diversity among populations of B. laevigata subsp. laevigata in NE Italy. None of the populations exhibited foliar hyperaccumulation of Cu, Zn, or Pb. The root-to-shoot accumulation rates for these metals were unchanged or decreased rather than enhanced in the metallicolous populations, in comparison with the non-metallicolous ones. Hyperaccumulation of Tl was confined to the population of the Cave del Predil mine. This population was genetically very distinct from the others, as demonstrated by AFLP-based cluster analysis. The two other mine populations did not surpass the threshold for Tl hyperaccumulation, but showed enhanced foliar Tl concentrations and root-to-shoot translocation rates, in comparison with the non-metallicolous populations. Genetic analysis suggested that adaptation to metalliferous soil must have been independently evolved in the metallicolous populations.

Biochar addition to an arsenic contaminated soil increases arsenic concentrations in the pore water but reduces uptake to tomato plants (Solanum lycopersicum L.).

Arsenic (As) concentrations in soil, soil pore water and plant tissues were evaluated in a pot experiment following the transplantation of tomato (Solanum lycopersicum L.) plantlets to a heavily As contaminated mine soil (~6000 mg kg(-1) pseudo-total As) receiving an orchard prune residue biochar amendment, with and without NPK fertiliser. An in-vitro test was also performed to establish if tomato seeds were able to germinate in various proportions of biochar added to nutrient solution (MS). Biochar significantly increased arsenic concentrations in pore water (500 µg L(-1)-2000 µg L(-1)) whilst root and shoot concentrations were significantly reduced compared to the control without biochar. Fruit As concentrations were very low (<3 µg kg(-1)), indicating minimal toxicity and transfer risk. Fertilisation was required to significantly increase plant biomass above the control after biochar addition whilst plants transplanted to biochar only were heavily stunted and chlorotic. Given that increasing the amount of biochar added to nutrient solution in-vitro reduced seed germination by up to 40%, a lack of balanced nutrient provision from biochar could be concluded. In summary, solubility and mobility of As were increased by biochar addition to this soil, but uptake to plant was reduced, and toxicity-transfer risk was negligible. Therefore leaching rather than food chain transfer appears the most probable immediate consequence of biochar addition to As contaminated soils.