Intensive agricultural management-induced subsurface accumulation of water-extractable colloidal P in a Vertisol

Abstract. Long-term excessive application of mineral fertilizer leads to phosphorus (P) accumulation, increasing the risk of P migration and loss from the soil profile. The colloids in the soil profile are important carriers for P migration due to their high P adsorption and transport capacity. It is not clearly understood how colloidal P (CP) is distributed in subsoils (<1.2 m) of a Vertisol, contributing to subsurface P loss. Understanding the depth sequence distribution and speciation of colloidal P in the soil profile is critical for a comprehensive assessment of P loss. In this study, water-extractable colloids (WECs) with the size of 0.35–2 µm were obtained from a 0–120 cm soil profile by a sedimentation and centrifugation scheme. The dissolved reactive P (DRP) and dissolved total P (DTP) in soil supernatant with particle sizes <0.35 µm were measured by molybdate blue colorimetry. Solution 31P nuclear magnetic resonance (NMR) and P K-edge XANES (X-ray absorption near-edge structure) were used to characterize the species and distribution of CP in the soil profile of fertilized farmland. Total and available P in bulk soil and colloids decreased with soil depth. The organic P (OP) contained 97–344 mg kg−1 per bulk soil and 110–630 mg kg−1 per WEC. The OP in soil profile consists of orthophosphate mono-esters and diesters primarily according to NMR results. It suggested that OP in WECs from subsoils might be affected by the translocation of CP from surface soils, probably due to soil acidification and preferential flow caused by swelling–shrinkage clays, including montmorillonite and nontronite detected by X-ray powder diffractometer (XRD) results. Additionally, the more negative zeta potential of surface soil colloids suggests the high mobility of colloidal P towards the subsoils. The CP concentration for <2 µm was about 38–93 mg P kg−1 per bulk soil, which is 6–37 times that of DRP, suggesting that CP plays a dominant role in P transport within the soil profile. The relatively small fraction of orthophosphate diesters suggests limited P assimilation by microorganisms for the accumulation of WECs containing organically bound P in subsoils. The P K-edge XANES results indicated that the proportions of Al-P, Fe-P, and inositol hexakisphosphate (IHP) of WECs decreased, but hydroxyapatite (HAP) increased with soil depth. This study showed that inorganic and organic P migrated from the surface to deeper layers along the soil profile, with soil colloids having a significant effect on P migration from both surface and subsurface layers. The findings have an important significance for soil P migration evaluation and agricultural non-point source pollution control in Vertisols.