Exploring spatial distribution and characterization of inorganic and organic phosphorus in temperate soils using NanoSIMS 

For a comprehensive understanding of the phosphorus (P) storage and cycling in temperate soils, it is necessary to explore further the bonding pathways of organic P (Po) and inorganic P (Pi) to mineral surfaces and soil organic matter (SOM), and their interconnections with organic carbon (OC) at a micro-scale other than conventional bulk analysis. In the past decade, nanoscale secondary ion mass spectrometry (NanoSIMS) has been increasingly recognized as a promising imaging technique to understand soil biogeochemical processes, particularly in exploring organo-mineral associations in soils at the microscale (Mueller et al., 2023). However, its application in studying P, and the identification and distinction of Po and Pi remains challenging, hindering a comprehensive understanding of the P cycling in soils. In our study, four temperate soil types, including Cambisol, Luvisol, Phaeozem and Fluvisol, were taken from Bavarian Forest in South-East Germany. The pH of these soils ranges from 5.4 to 6.3, with poor to medium P stocks but distinct Po stocks in fine fractions (<20 μm). Previous bulk studies have hinted at different pathways in P bonding to mineral surfaces and SOM. NanoSIMS was employed to further explore and visualize these bonding pathways. Recent advancements in NanoSIMS technology, particularly improved O- sources for cation detection and the capability for 31P- and 31P16O2- detection enable us to identify and distinguish Po and Pi at a microscale by 31P16O2-/31P- ratio, in which a lower ratio in specific areas corresponds to a more dominant presence of Po, and vice versa. From NanoSIMS images, preliminary results reveal that a proportion of Po associates with either clay minerals or Fe (hydr)oxdies without assimilating into SOM. This Po fraction is suspected to originate from highly decomposed SOM, where N has either been assimilated by microorganisms or leached away, and Po is stabilized to mineral surfaces due to strong bonding strength. In contrast, the Po assimilated into SOM is associated with various cations, including Ca, Al and Fe, which may suggest the origin from particulate organic matter. Interestingly, the fine plant residue is depleted in Po in the fine fraction. In conclusion, our study provides valuable insights into distinguishing different bonding pathways of these P forms within clay minerals, Fe (hydro)oxides, and SOM by using advanced NanoSIMS data, and emphasizes the interconnection with OC and Po and Pi in the fine fraction. Reference: Mueller, C. W., Hoeschen, C., Koegel-Knabner, I., 2023. Understanding of soil processes at the microscale—Use of NanoSIMS in soil science. Encyclopedia of Soils in the Environment (Second Edition). Elsevier. 10.1016/B978-0-12-822974-3.00045-8