Forms of Soil Phosphorus Accumulation in Grassland Soils

Australian soils are generally low in phosphorus (P) by world standards and require applied P to reduce this limitation on plant growth. In grazing systems P is deposited on the soil surface from fertiliser, livestock excretion and senescing pasture. Phosphate occurs in many forms in soils. Because of rising fertiliser prices there is growing interest in assessing and improving the availability of accumulated soil P. The objective of the research described here was to identify and quantify the forms of P in soils under permanent grasslands with a wide range of soil P status

Organic chemistry insights for the exceptional soil carbon storage of the seagrass Posidonia australis

The high organic carbon (OC) stores in seagrass meadows have led to their recognition as significant Blue Carbon sinks, though the diagenetic conditions that enable OC retention in seagrass soils remain poorly understood. In this study, seagrass soils were sampled from a Posidonia australis meadow in Oyster Harbour (Albany; south-western Australia) to investigate the preservation of sedimentary OC. We analysed soil characteristics (colour, grain size and redox potential), radiocarbon age, and characterised the soil organic matter (OM) using solid state CP/MAS 13C NMR spectroscopy to examine the preservation of OM down the soil profile. There was minimal change in organic composition over 1,700 years of accumulation, indicating long-term OM preservation. Primarily, this preservation appears to be driven by the recalcitrance of seagrass detritus buried in anoxic soils. The majority (70–83%) of total sedimentary OM comprised components directly attributable to seagrass origins (lignin, carbohydrate and black carbon-like matter), while the remainder consisted mostly of protein, some of which may have been present in seagrass biomass, along with likely contributions from algae and microbes. Although black carbon originates from organic matter combustion, here we provide evidence that the 13C NMR signal identified as black carbon-like matter in our soils is possibly associated with seagrass-derived organic matter consisting of degraded lignin products or other non-pyrogenic aromatics. The increase in the relative abundance of this black carbon-like matter with aging suggests its selective preservation. The relative abundances of carbohydrates significantly decreased with age down core (i.e. they appeared to be selectively decomposed), while lignin and protein did not show any quantitative changes in relative abundance (non-selective preservation). These findings demonstrate the exceptional preservation of P. australis derived OC, which contributes to our understanding of the higher OC storage capacity of Posidonia compared to other seagrass species. © 2020 Elsevier Lt

The fate of fertiliser P in soil under pasture and uptake by subterraneum clover: a field study using ³³P-labelled single superphosphate

Background and aims: Single superphosphate (SSP) is a major source of phosphorus (P) used in grazing systems to improve pasture production. The aim of this experiment was to determine the fate of fertiliser P in clover pastures under field conditions. Methods: A procedure was developed to radiolabel SSP granules with a ³³P radiotracer, which was then applied to the soil surface (equivalent to ~12 kg P ha‾¹) of a clover pasture. Recovery of fertiliser P was determined in clover shoots, fertiliser granules and soil fractions (surface layer: 0-4 cm and sub-surface layer: 4-8cm). Results: The P diffusion patterns of the ³³P-labelled SSP granules were not significantly different to those of commercial SSP granules (P > 0.05). Recovery of fertiliser P in clover shoots was 30-35 %. A considerable proportion of the fertiliser P (~28 %) was recovered in the surface soil layer and was largely inorganic P. Conclusions: Recovery of fertiliser P by clover plants was up to 35 % in the year of application. Much of the fertiliser P in soil fractions was inorganic P, which highlights the importance of inorganic P forms and dynamics in soils under clover pasture on a single season timeframe at these sites

Control of the pore size distribution and its spatial homogeneity in particulate activated carbon

There are circumstances where it is desirable to achieve a particular, optimal, pore size distribution (PSD) in a carbon, including in the molecular sieving, gas storage, CO2-capture and electrochemical energy storage. Activation protocols that cycle a carbon a number of times between a low-temperature oxygen chemisorption process and a higher temperature pyrolysis process have been proposed as a means of yielding such desired PSDs. However, it is shown here that for PFA-based char particles of ∼100 μm in size, only the super-micropores are substantially developed under such an activation protocol, with the ultra-micropores being substantially un-touched. It is also shown that a typical CO2-activation process yields similar control over PSD development. As this process is nearly 15 times faster than the cyclic-O2 protocol and yields larger pore volumes and areas for a given level of conversion, it is to be preferred unless spatial homogeneous porosity within the particles is also desired. If such homogeneity is desired, it is shown here that CO2 activation should continue to be used but at a rate of around one-tenth the typical; this slow rate also has the advantage of producing pore volumes and areas substantially greater than those obtained using the other activation protocols.CH acknowledges a joint scholarship provided by China Scholarship Council (CSC) and the University of Adelaide. SS acknowledges the award of International Postgraduate Research Scholarship (IPRS) from the University of Adelaide. SHM acknowledges the award of a President’s Scholarship from the University of South Australia. The support of the Australian Research Council Discovery Program (DP110101293) is also gratefully acknowledged

Frequency Versus Quantity: Phenotypic Response of Two Wheat Varieties to Water and Nitrogen Variability

Due to climate change, water availability will become increasingly variable, affecting nitrogen (N) availability. Therefore, we hypothesised watering frequency would have a greater impact on plant growth than quantity, affecting N availability, uptake and carbon allocation. We used a gravimetric platform, which measures the unit of volume per unit of time, to control soil moisture and precisely compare the impact of quantity and frequency of water under variable N levels. Two wheat genotypes (Kukri and Gladius) were used in a factorial glasshouse pot experiment, each with three N application rates (25, 75 and 150mgNkg−1 soil) and five soil moisture regimes (changing water frequency or quantity). Previously documented drought tolerance, but high N use efficiency, of Gladius as compared to Kukri provides for potentially different responses to N and soil moisture content. Water use, biomass and soil N were measured. Both cultivars showed potential to adapt to variable watering, producing higher specific root lengths under low N coupled with reduced water and reduced watering frequency (48h watering intervals), or wet/dry cycling. This affected mineral N uptake, with less soil N remaining under constant watering × high moisture, or 48h watering intervals × high moisture. Soil N availability affected carbon allocation, demonstrated by both cultivars producing longer, deeper roots under low N. Reduced watering frequency decreased biomass more than reduced quantity for both cultivars. Less frequent watering had a more negative effect on plant growth compared to decreasing the quantity of water. Water variability resulted in differences in C allocation, with changes to root thickness even when root biomass remained the same across N treatments. The preferences identified in wheat for water consistency highlights an undeveloped opportunity for identifying root and shoot traits that may improve plant adaptability to moderate to extreme resource limitation, whilst potentially encouraging less water and nitrogen use

Aromaticity and degree of aromatic condensation of char

The aromatic carbon structure is a defining property of chars and is often expressed with the help of two concepts: (i) aromaticity and (ii) degree of aromatic condensation. The varying extent of these two features is assumed to largely determine the relatively high persistence of charred material in the environment and is thus of interest for e.g. biochar characterization or carbon cycle studies. Consequently, a variety of methods has been used to assess the aromatic structure of chars, which has led to interesting insights but has complicated the comparison of data acquired with different methods. We therefore used a suite of seven methods (elemental analysis, MIR spectroscopy, NEXAFS spectroscopy, 13C NMR spectroscopy, BPCA analysis, lipid analysis and helium pycnometry) and compared 13 measurements from them using a diverse sample set of 38 laboratory chars. Our results demonstrate that most of the measurements could be categorized either into those which assess aromaticity or those which assess the degree of aromatic condensation. A variety of measurements, including relatively inexpensive and simple ones, reproducibly captured the two aromatic features in question, and data from different methods could therefore be compared. Moreover, general patterns between the two aromatic features and the pyrolysis conditions were revealed, supporting reconstruction of the highest heat treatment temperature (HTT) of char

Paramagnetic Effects on Solid State Carbon-13 Nuclear Magnetic Resonance Spectra of Soil Organic Matter

Copyright © 2002 American Society of Agronomy, Crop Science Society of America, and Soil Science Society of AmericaReceived for publication June 2, 2000. The effects of paramagnetic species on solid state 13C nuclear magnetic resonance (NMR) spectra were quantified in a series of doping experiments. The degree of signal loss caused by paramagnetic metals was shown to depend not only on the quantity, but also on the nature of the paramagnetic species, as well as the intimacy of contact with the organic substrate and the type of NMR experiment. Two mechanisms of signal loss were distinguished—signal loss via loss of magnetic field homogeneity, which affects all 13C nuclei in a sample, and signal loss via interaction between electronic and nuclear spins, the effects of which were localized to the close environment of the paramagnetic species. Loss of field homogeneity is important for manganese species, but not for copper species, and is equally important for both cross polarization and Bloch decay experiments. The interaction between electronic and nuclear spins is highly dependent on the spin-lattice relaxation rate constant of the free electron (T1e), as cations with very short T1e values (e.g., Pr3+) cause less signal loss than cations with longer T1e values (e.g., Cu2+, Mn2+). Cross polarization spectra are shown to be more susceptible than Bloch decay spectra to this mechanism of signal loss. Signal loss and increased relaxation rates brought about by paramagnetic species can be used to provide information on soil organic matter (SOM) heterogeneity in the submicron range. This is demonstrated for SOM doped with paramagnetic cations where selective signal loss and increased relaxation rates are used to determine the nature of cation exchange sites.Ronald J. Smernik and J. Malcolm Oade

Facile decomposition of phytate in the solid-state: Kinetics and decomposition pathways

<p></p> <p>The thermal decomposition of <i>myo</i>-inositol hexakisphosphate (phytate) in the solid state and in aqueous solution was investigated using ³¹P NMR spectroscopy. The progression of phytate decomposition was consistent with facile thermal dephosphorylation resulting in a cascading mixture of lower order inositol phosphates with similar, but not identical, trajectories in the solid state and in aqueous solution. In both states, phytate decomposition was well described by a simple exponential decay function, consistent with first order kinetics. At 60°C the reaction proceeded more rapidly in the solid state (<i>k</i> = 2.03 × 10⁻⁴ min⁻¹; t_1/2 = 2.4 days) than in aqueous solution (pH 3.84; <i>k =</i> 0.387 × 10⁻⁴ min⁻¹; t_1/2 = 12.4 days). In the solid state at 80°C (<i>k =</i> 19.6 × 10⁻⁴ min⁻¹; t_1/2 = 5.9 h) and 95°C (<i>k =</i> 106 × 10⁻⁴ min⁻¹; t_1/2 = 65.4 min) phytate loss also closely followed an exponential decay function. We hypothesise the rapid thermal decomposition is due to an impurity present in the phytate source that acts as a catalyst for facile transfer of the phospho (H₂PO₃ / HPO₃- / PO₃²⁻) group from phosphate esters to a range of oxygen functionalities present (water, alcohol groups, phosphate group). These reactions have important implications for understanding the stability of phytate under environmental conditions.</p