Samuel P. Stacey

Dissolution kinetics of macronutrient fertilizers coated with manufactured zinc oxide nanoparticles.

The solubility of Zn in Zn fertilizers plays an important role in the agronomic effectiveness of the fertilizer. On the basis of thermodynamics, zinc oxide (ZnO) nanoparticles (NPs) should dissolve faster and to a greater extent than bulk ZnO particles (equivalent spherical diameter >100 nm). These novel solubility features of ZnO NPs might be exploited to improve the efficiency of Zn fertilizers. In this study, we compared the Zn solubility and dissolution kinetics of ZnO nanoparticles and bulk ZnO particles coated onto two selected granular macronutrient fertilizers, urea and monoammonium phosphate (MAP). The main Zn species on coated MAP and urea granules were zinc ammonium phosphate and ZnO, respectively. Coated MAP granules showed greater Zn solubility and faster dissolution rates in sand columns compared to coated urea granules, which may be related to pH differences in the solution surrounding the fertilizer granules. The kinetics of Zn dissolution was not affected by the size of the ZnO particles applied for coating of either fertilizer type, possibly because solubility was controlled by formation of the same compounds irrespective of the size of the original ZnO particles used for coating.

Root Uptake of Lipophilic Zinc-Rhamnolipid Complexes

This study investigated the formation and plant uptake of lipophilic metal-rhamnolipid complexes. Monorhamnosyl and dirhamnosyl rhamnolipids formed lipophilic complexes with copper (Cu), manganese (Mn), and zinc (Zn). Rhamnolipids significantly increased Zn absorption by Brassica napus var. Pinnacle roots in (65)Zn-spiked ice-cold solutions, compared with ZnSO4 alone. Therefore, rhamnolipid appeared to facilitate Zn absorption via a nonmetabolically mediated pathway. Synchrotron XRF and XAS showed that Zn was present in roots as Zn-phytate-like compounds when roots were treated with Zn-free solutions, ZnSO4, or Zn-EDTA. With rhamnolipid application, Zn was predominantly found in roots as the Zn-rhamnolipid complex. When applied to a calcareous soil, rhamnolipids increased dry matter production and Zn concentrations in durum (Triticum durum L. cv. Balcali-2000) and bread wheat (Triticum aestivum L. cv. BDME-10) shoots. Rhamnolipids either increased total plant uptake of Zn from the soil or increased Zn translocation by reducing the prevalence of insoluble Zn-phytate-like compounds in roots.

Fate of Zinc Oxide Nanoparticles Coated onto Macronutrient Fertilizers in an Alkaline Calcareous Soil

Zinc oxide (ZnO) nanoparticles may provide a more soluble and plant available source of Zn in Zn fertilizers due to their greater reactivity compared to equivalent micron- or millimetre-sized (bulk) particles. However, the effect of soil on solubility, spatial distribution and speciation of ZnO nanoparticles has not yet been investigated. In this study, we examined the diffusion and solid phase speciation of Zn in an alkaline calcareous soil following application of nanoparticulate and bulk ZnO coated fertilizer products (monoammonium phosphate (MAP) and urea) using laboratory-based x-ray techniques and synchrotron-based μ-x-ray fluorescence (μ–XRF) mapping and absorption fine structure spectroscopy (μ–XAFS). Mapping of the soil-fertilizer reaction zones revealed that most of the applied Zn for all treatments remained on the coated fertilizer granule or close to the point of application after five weeks of incubation in soil. Zinc precipitated mainly as scholzite (CaZn2(PO4)2.2H2O) and zinc ammonium phosphate (Zn(NH4)PO4) species at the surface of MAP granules. These reactions reduced dissolution and diffusion of Zn from the MAP granules. Although Zn remained as zincite (ZnO) at the surface of urea granules, limited diffusion of Zn from ZnO-coated urea granules was also observed for both bulk and nanoparticulate ZnO treatments. This might be due to either the high pH of urea granules, which reduced solubility of Zn, or aggregation (due to high ionic strength) of released ZnO nanoparticles around the granule/point of application. The relative proportion of Zn(OH)2 and ZnCO3 species increased for all Zn treatments with increasing distance from coated MAP and urea granules in the calcareous soil. When coated on macronutrient fertilizers, Zn from ZnO nanoparticles (without surface modifiers) was not more mobile or diffusible compared to bulk forms of ZnO. The results also suggest that risk associated with the presence of ZnO NPs in calcareous soils would be the same as bulk sources of ZnO.

Selenate-Enriched Urea Granules Are a Highly Effective Fertilizer for Selenium Biofortification of Paddy Rice Grain

This study examined the effects of applied selenium (Se) species, time of application, method of application, and soil water management regimen on the accumulation of Se in rice plants. Plants were grown to maturity in a temperature- and humidity-controlled growth chamber using three water management methods: field capacity (FC), submerged until harvest, and submerged and drained 2 weeks before harvest. Two Se species, selenate (SeO4(2-)) and selenite (SeO3(2-)), were applied at a rate equivalent to 30 g ha(-1). Four application methods were employed as follows: (i) Se applied at soil preparation, (ii) Se-enriched urea granules applied to floodwater at heading; (iii) foliar Se applied at heading; and (iv) fluid fertilizer Se applied to soil or floodwater at heading. Total Se concentrations in rice grains, husks, leaves, culms, and roots were measured, as well as Se speciation in grains from the Se-enriched urea granule treatment. Highest Se concentrations in the grain occurred with SeO4(2-) and with fertilizer applied at heading stage; SeO4(2-)-enriched urea granules applied at heading increased grain Se concentrations 5-6-fold (by 450-600 μg kg(-1)) compared to the control (no fertilizer Se applied) in all water treatments. Under paddy conditions other Se fertilization strategies were much less effective. Drainage before harvesting caused Se to accumulate in/on rice roots, possibly through adsorption onto iron plaque on roots. Rice grains contained Se mainly in the organic form as selenomethionine (SeM), which comprised >90% of the total grain Se in treatments fertilized with SeO4(2-)-enriched urea granules. The results of this study clearly show that of the fertilizer strategies tested biofortification of Se in rice grains can best be achieved in lowland rice by broadcast application of SeO4(2-)-enriched urea granules to floodwater at heading stage.

X-ray fluorescence microscopy of zinc localization in wheat grains biofortified through foliar zinc applications at different growth stages under field conditions

AimBiofortification of wheat with zinc (Zn) through foliar Zn application has been proposed as an agronomic strategy to increase grain Zn concentration, which could serve as a nutritional intervention in regions with dietary Zn deficiency.MethodsBread wheat (Triticum aestivum L.) was biofortified through foliar Zn applications at different growth stages. The concentration of Zn and associated micronutrient in harvested whole grains was determined by ICP-OES. Synchrotron-based X-ray fluorescence microscopy (XFM) was then used to investigate the localization of Zn and associated micronutrients in cross sections of these grains.ResultsThe concentration of Zn and other micronutrients (Mn, Fe, and Cu) was higher in grains treated with foliar Zn during grain-filling (early milk/dough) than those treated at stem elongation. The increase in Zn concentration of wheat grain with foliar application during grain-filling can be attributed to the intense localization of Zn in the aleurone layer, modified aleurone, crease tissue, vascular bundle, and endosperm cavity, and to a modest localization in endosperm, which is the most dominant grain tissue. These tissues and the Zn they contain are presumed to remain after milling and can potentially increase the Zn concentration in wheat flour.ConclusionsBy using XFM, it was shown that foliar Zn spray represents an important agronomic tool for a substantial Zn enrichment of different fractions of wheat grain, especially the endosperm. Further investigation of the chemical speciation of Zn in the endosperm is recommended to assess Zn bioavailability in harvested whole grain of wheat that has been biofortified through different timing of foliar Zn application.

Micronutrient Deficiencies in Australian Field Crops

Australia’s ancient landscape has soils of exceptionally low fertility and deficiencies of all known nutrients have been recorded. Deficiencies of Mo and Zn are most widespread, being common on acid and alkaline soils respectively. Zinc deficiency is notable for being the most widely distributed micronutrient problem globally as well as in Australia, occurring on all soil classes, acid and alkaline, sandy and clayey, humid and arid, and in hot and cold growing seasons. Many Australian soils are affected by the presence of fine, free lime in the form of shellgrit blown up over the continent when sea levels were low during the last ice age; such soils, especially the more sandy types are low in micronutrient cations, Fe, Zn, Mn, Cu and/or Co. Multiple nutrient deficiencies are common, giving rise to a wealth of nutrient interaction effects. Interactions between two or more micronutrients and between microand macro-nutrients are agronomically and economically important. The classical micronutrient sensitivities reported elsewhere are also seen in Australia, but importantly, breeding has been carried out for tolerance to deficient soils in the major cereal crops, as well as tolerance to the common nutrient toxicities, the latter in common with activities in many parts of the world. The first deliberately bred cereal variety (barley) tolerant to Mn deficiency was released in South Australia in 2004. An important feature of the agronomy of micronutrients is the yield benefit in micronutrient-deficient soils of sowing seeds with a high micronutrient density. The use of plant analysis for diagnosis is almost always warranted as some crop varieties may lose much yield potential before symptoms of some micronutrient deficiencies appear. Recent research in South Australia has demonstrated that on calcareous soils, multi-nutrient fluid fertilisers have provided more efficient responses to both macronutrients and micronutrients than granular fertilizers.

Responses of tomato var. Tiny Tom to application of copper and zinc fertilizers in three limed tropical peat soils of Sarawak

We assessed the response of the tomato variety “Tiny Tom” to the application of copper (Cu) and zinc (Zn) fertilizers in three tropical peat soils of Sarawak: mixed swamp forest, Alan forest and Padang Alan forest. Limed soils were used because peat soils in their natural condition are unsuitable to sustain healthy growth of most crops. Yield responses were correlated with added Cu and Zn using Mitscherlich model. Adequate levels of applied Cu and Zn were calculated as those which resulted in 90% of the maximum obtainable shoot dry weight. Application of Cu and Zn significantly (P ≤ 0.05) increased the shoot dry weight and the shoot Cu and Zn concentrations of tomato. Application of the equivalent of 8.3 kg Cu and 5.2 kg Zn per ha was required to achieve 90% of the maximum shoot dry weight. In tomato shoots, the critical concentration for Cu was 18 mg/kg and for Zn, 92 mg/kg. The corresponding concentrations for diethylenetriaminepentaaceticacid (DTPA) extractable Cu and Zn in the soils were 2.3 mg Cu kg −1 and 3.6 mg Zn kg −1 . However, the addition of Cu fertilizer also increased Zn uptake by tomato plant, probably by displacing native Zn that was weakly sorbed to the soil solid phase.