Zinc-Intercalated Halloysite Nanotubes as Potential Nanocomposite Fertilizers with Targeted Delivery of Micronutrients.

This study reports on the development of nanocomposites utilizing a mineral inhibitor and a micronutrient filler. The objective was to produce a slow release fertilizer, with zinc sulfate as the filler and halloysite nanotubes as the inhibitor. The study seeks to chemically activate the intercalation of zinc into the macro-, meso-, and micropores of the halloysite nanotubes to enhance their performance. As a result, we obtained three nanocomposites in zinc sulfate solution with concentrations of 2%, 20%, and 40%, respectively, which we named Hly-7Å-Zn2, Hly-7Å-Zn20, and Hly-7Å-Zn40. We investigated the encapsulation of zinc sulfate in halloysite nanotubes using X-ray diffraction analysis, transmission electron spectroscopy, infrared spectroscopy (FTIR), and scanning electron microscopy with an energy-dispersive spectrometer. No significant changes were observed in the initial mineral parameters when exposed to a zinc solution with a concentration of 2 mol%. It was proven that zinc was weakly intercalated in the micropore space of the halloysite through the increase in its interlayer distance from 7.2 to 7.4. With an increase in the concentration of the reacted solution, the average diameter of the nanotubes increased from 96 nm to 129 nm, indicating that the macropore space of the nanotubes, also known as the "site", was filled. The activated nanocomposites exhibit a maximum fixed content of adsorbed zinc on the nanotube surface of 1.4 wt%. The TEM images reveal an opaque appearance in the middle section of the nanotubes. S SEM images revealed strong adhesion of halloysite nanotubes to plant tissues. This property guarantees prolonged retention of the fertilizer on the plant surface and its resistance to leaching through irrigation or rainwater. Surface spraying of halloysite nanotubes offers accurate delivery of zinc to plants and prevents soil and groundwater contamination, rendering this fertilizer ecologically sound. The suggested approach of activating halloysite with a zinc solution appears to be a possible route forward, with potential for the production of tailored fertilizers in the days ahead.

Preparation, Features, and Efficiency of Nanocomposite Fertilisers Based on Glauconite and Ammonium Dihydrogen Phosphate.

This paper studies the chemical and mechanochemical preparation of glauconite with ammonium dihydrogen phosphate (ADP) nanocomposites with a ratio of 9:1 in the vol.% and wt.%, respectively. The methods include X-ray diffraction analysis, scanning electron microscope with energy-dispersive X-ray spectroscopy, transmission electron microscopy, infrared spectroscopy, and differential thermal analysis with a quadruple mass spectrometer. The manufactured nanocomposites keep the flaky glauconite structure. Some glauconite unit structures have been thickened due to minimal nitrogen (ammonium) intercalation into the interlayer space. The globular, granular, or pellet mineral particles of nanocomposites can be preserved via chemical techniques. Globular and micro-aggregate particles in nanocomposites comprise a thin film of adsorbed ADP. The two-step mechanochemical method makes it possible to slightly increase the proportion of adsorbed (up to 3.2%) and intercalated (up to 6.0%) nutrients versus chemical ways. Nanocomposites prepared via chemical methods consist of glauconite (90%), adsorbed (1.8-3.6%), and intercalated (3.0-3.7%) substances of ADP. Through the use of a potassium-containing clay mineral as an inhibitor, nitrogen, phosphorus, and potassium (NPK), nanocomposite fertilisers of controlled action were obtained. Targeted and controlled release of nutrients such as phosphate, ammonium, and potassium are expected due to various forms of nutrients on the surface, in the micropores, and in the interlayer space of glauconite. This is confirmed via the stepwise dynamics of the release of ammonium, nitrate, potassium, and phosphate from their created nanocomposites. These features of nanocomposites contribute to the stimulation of plant growth and development when fertilisers are applied to the soil.

Organic matter composition and greenhouse gas production of thawing subsea permafrost in the Laptev Sea.

Subsea permafrost represents a large carbon pool that might be or become a significant greenhouse gas source. Scarcity of observational data causes large uncertainties. We here use five 21-56 m long subsea permafrost cores from the Laptev Sea to constrain organic carbon (OC) storage and sources, degradation state and potential greenhouse gas production upon thaw. Grain sizes, optically-stimulated luminescence and biomarkers suggest deposition of aeolian silt and fluvial sand over 160 000 years, with dominant fluvial/alluvial deposition of forest- and tundra-derived organic matter. We estimate an annual thaw rate of 1.3 ± 0.6 kg OC m-2 in subsea permafrost in the area, nine-fold exceeding organic carbon thaw rates for terrestrial permafrost. During 20-month incubations, CH4 and CO2 production averaged 1.7 nmol and 2.4 µmol g-1 OC d-1, providing a baseline to assess the contribution of subsea permafrost to the high CH4 fluxes and strong ocean acidification observed in the region.

Patterning GaSe by High-Powered Laser Beams.

We report the high-powered laser modification of the chemical, physical, and structural properties of the two-dimensional (2D) van der Waals material GaSe. Our results show that contrary to expectations and previous reports, GaSe at the periphery of a high-power laser beam does not entirely decompose into Se and Ga2O3. In contrast, we find unexpectedly that the Raman signal from GaSe gets amplified around regions where it was not expected to exist. Atomic force microscopy (AFM), dielectric force microscopy (DFM), scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDX) results show that laser irradiation induces the formation of nanoparticles. Our analyses demonstrate that, except for a fraction of Ga2Se3, these nanoparticles still belong to the GaSe phase but possess different electrical and optical properties. These changes are evidenced in the increased Raman intensity attributed to the near-resonance conditions with the Raman excitation laser. The elemental analysis of nanoparticles shows that the relative selenium content increased to as much as 70% from a 50:50 value in stoichiometric GaSe. This elemental change is related to the formation of the Ga2Se3 phase identified by Raman spectroscopy at some locations near the edge. Further, we exploit the localized high-power laser processing of GaSe to induce the formation of Ag-GaSe nanostructures by exposure to a solution of AgNO3. The selective reaction of AgNO3 with laser-irradiated GaSe gives rise to composite nanostructures that display photocatalytic activity originally absent in the pristine 2D material. The photocatalytic activity was investigated by the transformation of 4-nitrobenzenethiol to its amino and dimer forms detected in situ by Raman spectroscopy. This work improves the understanding of light-matter interaction in layered systems, offering an approach to the formation of laser-induced composites with added functionality.

The correlation between electrical conductivity and second-order Raman modes of laser-reduced graphene oxide.

Raman spectroscopy is the tool of choice in the physicochemical investigation of carbon nanomaterials. However, Raman analysis of graphene oxide (GO) is lagging in comparison to the rich information gained in the case of carbon nanotubes and graphene. Here, we carried out a joint current sensing atomic force microscopy (CSAFM) and Raman spectroscopy investigation of laser-reduced GO. Reduced graphene oxide (rGO) was obtained under different laser powers in the range from 0.1 to 10 mW (532 nm). We compare the Raman spectra and the electrical conductivity at the nanoscale obtained by current sensing atomic force microscopy. Our analysis shows that three bands in the second-order region (2D, D + G, 2G), in the range from 2500 to 3200 cm-1, are uniquely sensitive to the degree of reduction. Moreover, we found that the changes in peak area ratios AD+G/AD and A2G/AD show a direct correlation with the electrical resistance of rGO. We establish an optical micro-spectroscopy way to assess the degree of reduction in laser-reduced GO. These new insights provide a convenient and useful way to investigate the reduction of rGO from the fitting analysis of Raman spectra, becoming a useful tool in fundamental research and the development of rGO-based microdevices.

Non-invasive monitoring of red beet development.

Agricultural monitoring is required to enhance crop production, control plant stress, and predict pests and crop infection. Apart from monitoring the external influences, the state of the plant itself must be tracked. However, the modern methods for plant analysis are expensive and require plants processing often in a destructive way. Optical spectroscopy can be used for the non-invasive monitoring requiring no consumables, and little to none sample preparation. In this context, we found that the red beet growth can be monitored by Raman spectroscopy. Our analysis shows that, as plants age, the rate of betalain content increases. This increase makes betalain dominate the whole Raman spectra over other plant components. The dominance of betalain facilitates its use as a molecular marker for plant growth. This finding has implications in the understanding of plant physiology, particularly important for greenhouse growth and the optimization of external conditions such as artificial illumination.