Desorption Kinetics of Legacy Soil Phosphorus: Implications for Non-Point Transport and Plant Uptake

Soil phosphorus (P) solubility and kinetics partly control dissolved P losses to surface water and uptake by plants. While previous studies have focused on batch techniques for measuring soil P desorption kinetics, flow-through techniques are more realistic because they simulate P removal from the system, akin to runoff, leaching, and plant uptake. The objectives were to measure soil P desorption by a flow-through technique at two flow rates and several batch methods, and utilize both for understanding how flow rate impacts the thermodynamics and kinetics of soil P desorption. Desorption obeyed first-order kinetics in two different phases: an initial rapid desorption phase followed by a gradual release. Desorption was limited by equilibrium and the kinetics of physical processes as demonstrated by an interruption test. Dilution-promoted desorption occurred with increasing cumulative volume, which increased desorption rate via first-order kinetics. The batch tests that simulated cumulative solution volume and time of flow-through were similar to the flow-through results; however, the batch methods overestimated the desorption rates due to less limitations to diffusion. Fast flow rates desorbed less P, but at a greater speed than slow flow rates. The differences were due to contact time, cumulative time, and solution volume, which ultimately controlled the potential for chemical reactions to be realized through physical processes. The interaction between these processes will control the quantity and rate of desorption that buffer P in non-point drainage losses and plant uptake.

Shape- and size- dependent desorption kinetics and surface acidity on nano-SnO2

The desorption kinetic parameters (the desorption activation energy (Ed) and the desorption pre-exponential factor (A)) and the surface acidity (the strength and number of acid sites) of spherical and octahedral...

A NIR-Based Study of Desorption Kinetics during Continuous Spin Freeze-Drying

The pharmaceutical industry is progressing toward the development of more continuous manufacturing techniques. At the same time, the industry is striving toward more process understanding and improved process control, which requires the implementation of process analytical technology tools (PAT). For the purpose of drying biopharmaceuticals, a continuous spin freeze-drying technology for unit doses was developed, which is based on creating thin layers of product by spinning the solution during the freezing step. Drying is performed under vacuum using infrared heaters to provide energy for the sublimation process. This approach reduces drying times by more than 90% compared to conventional batch freeze-drying. In this work, a new methodology is presented using near-infrared (NIR) spectroscopy to study the desorption kinetics during the secondary drying step of the continuous spin freeze-drying process. An inline PLS-based NIR calibration model to predict the residual moisture content of a standard formulation (i.e., 10% sucrose) was constructed and validated. This model was then used to evaluate the effect of different process parameters on the desorption rate. Product temperature, which was controlled by a PID feedback mechanism of the IR heaters, had the highest positive impact on the drying rate during secondary drying. Using a higher cooling rate during spin freezing was found to significantly increase the desorption rate as well. A higher filling volume had a smaller negative effect on the drying rate while the chamber pressure during drying was found to have no significant effect in the range between 10 and 30 Pa.

Hierarchical Mesoporous SSZ-13 Chabazite Zeolites for Carbon Dioxide Capture

Artificial carbon dioxide capture is an alternative method to remove the carbon dioxide already accumulated in the atmosphere as well as to stop its release at its large-scale emission points at the source, such as at power plants. However, new adsorbents are needed to make the approach feasible. For this purpose, in this study, hierarchical mesoporous-microporous chabazite-type zeolites were synthesised by applying a dual-templating method. The microporous zeolite structure-directing agent N,N,N-trimethyl-1-adamantanammonium hydroxide was combined with an organosilane mesopore-generating template, 3-(trimethoxysilyl)propyl octadecyl dimethyl ammonium chloride. Materials were characterised for their structural and textural properties and tested for their carbon dioxide capture capacity both in their original sodium form and in their proton-exchanged form by means of breakthrough curve analysis and sorption isotherms. The influence of template ratios on their structure, carbon dioxide capture, and capacity have been identified. All mesoporous materials showed fast adsorption-desorption kinetics due to a reduction in the steric limitations via the introduction of a meso range network of pores. The hierarchical zeolites are recyclable with a negligible loss in crystallinity and carbon dioxide capture capacity, which makes them potential materials for larger-scale application.

The Adsorption of Phosphate on Mica Surfaces

<p>The surface chemistry of the 001 face of cleaved mica sheets was studied with a view to understanding some of the fundamental processes underlying the phenomenon of fixation of phosphate by soils. Radiochemical techniques were developed to make quantitative studies of the adsorption, an important part of these being practical procedures for obtaining sufficient cleanliness and freedeom from airborne contamination. Lack of uniformity of adsorption, as shown by autoradiography, was taken to indicate contamination, and techniques were developed to avid this. Other techniques enabled the continuous monitoring of the sample during adsorption or desorption kinetic experiments. It was shown that adsorption of phosphate on the untreated mica sheets was low, but the adsorption was greatly enhanced if the mica had been treated with aqueous solutions of certain cations such as gallium, aluminium and iron. Form the measurement of the amount of phosphate adsorbed, as a function of the conditions of aluminium treatment, it was concluded that the phosphate could be absorbed by at least three different processes, all of which could be of importance in phosphate fixation by soils. As well as these processes, which occurred on clean, flat, mica surfaces, there were others, involving the edges of mica and sheets, and unknown, but probably organic, films on both mica and air-water surfaces. These could all be of comparable importance in soils. The kinetic measurements of phosphate adsorption and desorption on aluminium-treated mica indicated that many hours were required for attainment of equilibrium, and were quantitatively consistent with the hypothesis that in some cases the adsorption and desorption kinetics were controlled by diffusion of phosphate into particles of some material, possibly a hydrous oxide, adsorbed on the mica. The existence of such particles was supported by the fact that up to one phosphate molecule per two square Angstrom units of mica surface was adsorbed, (and this did not appear to be a value at which the surface was saturated.) Kinetic measurements of 67 Ga sorption processes were consistent with diffusion of gallium through a thin water film, with a diffusion coefficient several orders of magnitude lower than that of single ions in free solution. This may indicate that the gallium was adsorbing as particles, in agreement with the requirements of the phosphate experiments.</p>

The Adsorption of Phosphate on Mica Surfaces

<p>The surface chemistry of the 001 face of cleaved mica sheets was studied with a view to understanding some of the fundamental processes underlying the phenomenon of fixation of phosphate by soils. Radiochemical techniques were developed to make quantitative studies of the adsorption, an important part of these being practical procedures for obtaining sufficient cleanliness and freedeom from airborne contamination. Lack of uniformity of adsorption, as shown by autoradiography, was taken to indicate contamination, and techniques were developed to avid this. Other techniques enabled the continuous monitoring of the sample during adsorption or desorption kinetic experiments. It was shown that adsorption of phosphate on the untreated mica sheets was low, but the adsorption was greatly enhanced if the mica had been treated with aqueous solutions of certain cations such as gallium, aluminium and iron. Form the measurement of the amount of phosphate adsorbed, as a function of the conditions of aluminium treatment, it was concluded that the phosphate could be absorbed by at least three different processes, all of which could be of importance in phosphate fixation by soils. As well as these processes, which occurred on clean, flat, mica surfaces, there were others, involving the edges of mica and sheets, and unknown, but probably organic, films on both mica and air-water surfaces. These could all be of comparable importance in soils. The kinetic measurements of phosphate adsorption and desorption on aluminium-treated mica indicated that many hours were required for attainment of equilibrium, and were quantitatively consistent with the hypothesis that in some cases the adsorption and desorption kinetics were controlled by diffusion of phosphate into particles of some material, possibly a hydrous oxide, adsorbed on the mica. The existence of such particles was supported by the fact that up to one phosphate molecule per two square Angstrom units of mica surface was adsorbed, (and this did not appear to be a value at which the surface was saturated.) Kinetic measurements of 67 Ga sorption processes were consistent with diffusion of gallium through a thin water film, with a diffusion coefficient several orders of magnitude lower than that of single ions in free solution. This may indicate that the gallium was adsorbing as particles, in agreement with the requirements of the phosphate experiments.</p>

Graphene and Carbon Nanotubes Fibrous Composite Decorated with PdMg Alloy Nanoparticles with Enhanced Absorption–Desorption Kinetics for Hydrogen Storage Application

We describe a graphene and fibrous multiwall carbon nanotubes (f-MWCNT) composite film prepared by plasma-enhanced chemical vapor deposition for use as a suitable and possible candidate of hydrogen storage materials. A high storage capacity of 5.53 wt% has been obtained with improved kinetics. The addition of binary PdMg alloy nanoparticles to the surface of graphene-fibrous nanotubes composite films raised the storage capacity by 53% compared to the film without PdMg decorated nanoparticles. Additionally, the graphene/f-MWCNT composite film decorated with PdMg nanoparticles exhibited an enhanced hydrogen absorption–desorption kinetics. The fibrous structure of the MWCNTs, alongside graphene sheets within the film, creates an enormous active region site for hydrogen reaction. The addition of PdMg nanoparticles enhanced the reaction kinetics due to the catalytic nature of Pd, and increased the hydrogen content due to the high absorption capacity of Mg nanoparticles. The combination of Pd and Mg in a binary alloy nanoparticle enhanced the hydrogen capacity and absorption–desorption kinetics.