Effect of particle size of nanoscale zero-valent copper on inorganic phosphorus adsorption-desorption in a volcanic ash soil.

Zero-valent copper engineered nanoparticles (Cu-ENPs) released through unintentional or intentional actions into the agricultural soils can alter the availability of inorganic phosphorus (IP) to plants. In this study, we used adsorption-desorption experiments to evaluate the effect of particle size of 1% Cu-ENPs (25 nm and 40-60 nm) on IP availability in Santa Barbara (SB) volcanic ash soil. X-Ray Diffraction results showed that Cu-ENPs were formed by a mixture of Cu metallic and Cu oxides (Cu2O or/and CuO) species, while specific surface area values showed that Cu-ENPs/25 nm could form larger aggregate particles compared to Cu-ENPs/40-60 nm. The kinetic IP adsorption of SB soil without and with 1% Cu-ENPs (25 nm and 40-60 nm) followed the mechanism described by the pseudo-second-order (k2 = 0.45-1.13 x 10-3 kg mmol-1 min-1; r2 ≥ 0.999, and RSS ≤ 0.091) and Elovich (α = 14621.10-3136.20 mmol kg-1 min-1; r2 ≥ 0.984, and RSS ≤ 69) models. Thus, the rate-limiting step for IP adsorption in the studied systems was chemisorption on a heterogeneous surface. Adsorption equilibrium isotherms without Cu-ENPs were fitted well to the Freundlich model, while with 1% Cu-ENPs (25 nm and 40-60 nm), isotherms were described best by the Freundlich and/or Langmuir model. The IP relative adsorption capacity (KF) was higher with 1% Cu-ENPs/40-60 nm (KF = 110.41) than for 1% Cu-ENPs/25 nm (KF = 74.40) and for SB soil (KF = 48.17). This study showed that plausible IP retention mechanisms in the presence of 1% Cu-ENPs in SB soil were: i) ligand exchange, ii) electrostatic attraction, and iii) co-precipitate formation. The desorption study demonstrated that 1% Cu-ENPs/40-60 nm increased the affinity of IP in SB soil with a greater effect than 1% Cu-ENPs/25 nm. Thus, both the studied size ranges of Cu-ENPs could favor an accumulation of IP in volcanic ash soils.

Biochemical and Molecular Responses Underlying the Contrasting Phosphorus Use Efficiency in Ryegrass Cultivars.

Improving plant ability to acquire and efficiently utilize phosphorus (P) is a promising approach for developing sustainable pasture production. This study aimed to identify ryegrass cultivars with contrasting P use efficiency, and to assess their associated biochemical and molecular responses. Nine ryegrass cultivars were hydroponically grown under optimal (0.1 mM) or P-deficient (0.01 mM) conditions, and P uptake, dry biomass, phosphorus acquisition efficiency (PAE) and phosphorus utilization efficiency (PUE) were evaluated. Accordingly, two cultivars with high PAE but low PUE (Ansa and Stellar), and two cultivars with low PAE and high PUE (24Seven and Extreme) were selected to analyze the activity and gene expression of acid phosphatases (APases), as well as the transcript levels of P transporters. Our results showed that ryegrass cultivars with high PAE were mainly influenced by root-related responses, including the expression of genes codifying for the P transporter LpPHT1;4, purple acid phosphatase LpPAP1 and APase activity. Moreover, the traits that contributed greatly to enhanced PUE were the expression of LpPHT1;1/4 and LpPHO1;2, and the APase activity in shoots. These outcomes could be useful to evaluate and develop cultivars with high P-use efficiency, thus contributing to improve the management of P in grassland systems.

nZVI-Based Nanomaterials Used for Phosphate Removal from Aquatic Systems.

In the last decade, the application of nanoscale zero-valent iron (nZVI) has garnered great attention as an adsorbent due to its low cost, non-toxicity, high porosity, and BET-specific surface area. In particular, the immobilization of nZVI particles onto inorganic and organic substrates (nanocomposites) decreased its agglomeration, allowing them to be effective and achieve greater adsorption of pollutants than pristine nanoparticles (NPs). Although nZVI began to be used around 2004 to remove pollutants, there are no comprehensive review studies about phosphate removal from aquatic systems to date. For this reason, this study will show different types of nZVI, pristine nZVI, and its nanocomposites, that exist on the market, how factors such as pH solution, oxygen, temperature, doses of adsorbent, initial phosphate concentration, and interferents affect phosphate adsorption capacity, and mechanisms involved in phosphate removal. We determined that nanocomposites did not always have higher phosphate adsorption than pristine nZVI particles. Moreover, phosphate can be removed by nZVI-based nanoadsorbents through electrostatic attraction, ion exchange, chemisorption, reduction, complexation, hydrogen bonding, and precipitation mechanisms. Using the partition coefficient (PC) values, we found that sepiolite-nZVI is the most effective nanoadsorbent that exists to remove phosphate from aqueous systems. We suggest future studies need to quantify the PC values for nZVI-based nanoadsorbents as well as ought to investigate their phosphate removal efficiency under natural environmental conditions.

The effect of silicon supply on photosynthesis and carbohydrate metabolism in two wheat (Triticum aestivum L.) cultivars contrasting in response to phosphorus nutrition.

Phosphorus (P) deficiency affects agricultural systems by limiting crop quality and yield. Studies have suggested that silicon (Si) improves P uptake in plants grown under P deficiency. However, the effects of Si on photosynthesis and carbohydrate metabolism under P stress remain unclear. We performed a hydroponic study using two wheat cultivars with contrasting sensitivity to P deficiency (Púrpura, sensitive; Fritz, semi-tolerant) that were exposed to P (0, 0.01, or 0.1 mM) and Si (0 or 2 mM), and we evaluated the photosynthetic performance and metabolic alterations. In plants from the sensitive cultivar undergoing P deficiency, Si application increased sucrose levels, starch breakdown and length of shoots, and also improved plant dry weight. In Fritz (the semi-tolerant cultivar), Si exposure reduced P concentration, and increased shoot length and P use efficiency (PUE) under P shortage. Interestingly, Si application altered cell wall composition, which was associated with higher mesophyll conductance and net CO2 assimilation in Fritz plants grown under P stress. Together, our results indicate that under P deficiency, Si nutrition positively affects photosynthesis and carbohydrate levels in a genotype-dependent manner. Furthermore, these results suggest that Si plays an important role in maintaining high photosynthetic rates in wheat plants undergoing P deficiency.