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A wide range of methods are used to estimate the plant-availability of soil phosphorus (P). Published research has shown that the diffusive gradients in thin films (DGT) technique has a superior correlation to plant-available P in soils compared to standard chemical extraction tests. In order to identify the plantavailable soil P species, we combined DGT with infrared and P K- and L2,3-edge X-ray adsorption near edge structure (XANES) spectroscopy. This was achieved by spectroscopically investigating the dried binding layer of DGT devices after soil deployment. All three spectroscopic methods were able to distinguish between different kinds of phosphates (poly-, trimeta-, pyro- and orthophosphate) on the DGT binding layer. However, infrared spectroscopy was most sensitive to distinguish between different types of adsorbed inorganic and organic phosphates. Furthermore, intermediates of the time-resolved hydrolysis of trimetaphosphate in soil could be analyzed.
Phosphorus (P) is an essential element for all life forms, and P-availability thus an important driver of a functioning agriculture. However, phosphate rock resources for P-fertilizer production are only available in a few countries. Therefore, P-recovery from waste materials has become of increasing interest during the last decade and has been investigated worldwide. In order to characterize potential novel P-fertilizers made from recycled materials, a large array of P-compound characterizations, chemical extractions and growth experiments were performed. This review bundles the work carried out in that field over the last years. Overall, P-fertilizers from recycled materials show a broad range of P-compounds with very different chemical structure and solubility. Growth experiments performed to assess their fertilizing effects display high variations for most of the products. While these experiments have demonstrated that some fertilizers made of recycled materials may reach P effects in the same order of magnitude as water-soluble phosphate rock-based fertilizers, an important limitation in their interpretation is the fact that they often vary considerably in their experimental design. The existing data show clearly that standardization of growth experiments is urgently needed to achieve comparable results. Standard chemical extractants used to assess the chemical solubility of P-fertilizers were found to be of limited reliability for predicting plant P uptake. Therefore, alternative methods such as sequential fractionation, or the extraction of incubated soil/fertilizer mixtures with standard soil extractants or with P sink methods should be tested more intensively in the future to provide alternative options to predict the P-availability of fertilizers from recycled materials.
In Denmark, increasing amounts of woody biomass are being used for the production of renewable energy, resulting in more wood ashes being generated. While these materials have been mainly landfilled, wood ashes may also be utilised for fertilizing and liming purposes on top of soils. Pre-treatments involving hardening or granulation may be carried out prior to soil application. In this study, two Danish wood ash samples were hardened and/or granulated. Lab-hardening induced rapid changes in the shape of the acid neutralisation capacity curve of the ashes. Up-flow column tests, assuming local equilibrium conditions, were employed to investigate the leaching from pre-treated ashes. Granules and loose ashes demonstrated similar leaching behaviours, indicating that similar geochemical processes were governing their leaching. In comparison with untreated fresh ashes, the hardened ashes demonstrated reduced leaching of Ca, Ba, Pb and Zn with concentration levels generally below or close to the analytical limits of quantification; to the contrary, the leaching of As, P, Sb, Si, V and Mg was enhanced in the hardened ashes. The release of alkalinity was reduced by hardening. In general, all granules were barely breakable by finger-pinching and they could withstand one month of continuous leaching, preserving their overall shape. The solubility of phosphorous in neutral ammonium citrate indicated that about 30–51% of the total P content in the ash samples was released, suggesting that the ashes could be potentially valuable as P-fertiliser if applied onto soil.