Speciation of soil organic phosphorus: Steps from NMR spectra to bioavailability

Phosphorus (P) is an essential element for all life on Earth. Understanding P cycling is in the context of global change crucial both for modelling of global biogeochemical cycles and for agricultural productivity. Recently, concerns about the future of P fertilizer supply have prompted much research on soil P and method development. 31P Nuclear Magnetic Resonance (NMR) Spectroscopy has been used to analyse speciation of inorganic and of organic P species (Po), using in alkaline soil extracts1. The region containing signals from phosphomonoesters is particularly important because these compounds are considered biologically active, but there are still significant problems to be resolved particularly for this region of P NMR spectra, including: 1. Poor signal resolution often makes quantification of Po species in this region very challenging. 2. It is unclear if observed signals are due to free P species, or originate from P compounds bound to high-molecular weight soil matter. 3. The question needs to be addressed how signals observed in alkaline extracts relate to P species that were originally present in the soil. Here we present two approaches to address these problems:In a study of a 5000-year soil chronosequence in Northern Sweden2, we found that humus P composition barely changed, although time since fire varied up to 5000 years. We will present a new method to back-calculate original Po speciation from the observed composition. Results of this method indicate absence of “recalcitrant” Po species, and instead indicate that most Po was originally present as biologically active P metabolites, probably present in live soil organisms. We will discuss implication of these findings for P biogeochemistry.Second, we studied a diverse group of soils to address how the poorly resolved phosphomonoester region should best be analysed. Deconvolution techniques are required to handle the overlap, but a better understanding of the nature of the signals is required for reliable quantification. Based on combined analysis of 1D 31P NMR, 2D 1H-31P NMR and 31P linewidth measurements, we present a strategy for quantification of phosphomonoester species, as next step in linking observed Po speciation to P bioavailability. (1) Cade-Menun BJ, Preston CM (1996) A comparison of soil extraction procedures for 31P NMR spectroscopy. Soil Sci 161:770–785(2) Andrea G. Vincent, Jürgen Schleucher, Reiner Giesler, David A. Wardle (2022) Soil phosphorus forms show only minor changes across a 5000‑year‑old boreal wildfire chronosequence. Biogeochemistry (2022) 159:15–32  https://doi.org/10.1007/s10533-022-00910-2(3) Vestergren J, Vincent AG, Jansson M et al (2012) High-resolution characterization of organic phosphorus in soil extracts using 2D 1H–31P NMR correlation spectroscopy. Environ Sci Technol 46:3950–3956. https:// doi. org/ 10. 1021/ es204016h