Ganga Hettiarachchi

Phosphorus (P) dynamics in the soil subsurface are relatively unstudied, especially in forest soils, and may be important in areas with groundwater‐fed surface water bodies. Here, we use X‐ray absorption near‐edge P spectroscopy (P‐XANES) and X‐ray fluorescence microprobe mapping (µ‐XRF) to examine P speciation and co‐localization with Fe and Al as a function of depth in soils from coniferous and deciduous forests. P‐XANES revealed similar trends in P speciation with depth for both forest types, with Al‐P and Fe‐P being dominant, whereas Ca‐P and organic P were minor constituents. Correlation plots derived from µ‐XRF mapping revealed a strong correlation between P and both Fe and Al at all depths. At depths of up to 378 cm, a range that includes A, E, and B horizons, the relationships between P and Al/Fe were remarkably consistent, consisting of a population of P diffusely associated with Al/Fe, consistent with Fe‐ or Al‐adsorbed P, as well as P linearly correlated with Al/Fe in several discreet groupings, indicative of the presence of specific P compounds. At depths below 378 cm, the relationships between P and Al/Fe changed dramatically, with correlation plotting indicating the disappearance of any diffuse P:Al/Fe relationships. This change occurred concurrently with a decrease in oxalate extractable P, suggesting that the P present in this deep soil horizon may be present in a more stable form that is less available for transport, as well as potentially indicating that P adsorbed to Fe/Al did not readily pass through the overlaying Bw soil horizon.

Snowmelt runoff is a dominant pathway of phosphorus (P) losses from agricultural lands in cold climatic regions. Soil amendments effectively reduce P losses from soils by converting P to less soluble forms; however, changes in P speciation in cold climatic regions with fall‐applied amendments have not been investigated. This study evaluated P composition in soils from a manured field with fall‐amended alum (Al 2 (SO 4 ) 3 ·18H 2 O), gypsum (CaSO 4 ·2H 2 O), or Epsom salt (MgSO 4 ·7H 2 O) using three complementary methods: sequential P fractionation, scanning electron microscopy with energy‐dispersive X‐rays (SEM‐EDX) spectroscopy, and P K‐edge X‐ray absorption near‐edge structure spectroscopy (XANES). Plots were established in an annual crop field in southern Manitoba, Canada, with unamended and amended (2.5 Mg ha −1 ) treatments having four replicates in 2020 fall. Soil samples (0–10 cm) taken from each plot soon after spring snowmelt in 2021 were subjected to P fractionation. A composite soil sample for each treatment was analyzed using SEM‐EDX and XANES. Alum‐ and Epsom salt‐treated soils had significantly greater residual P fraction with a higher proportion of apatite‐like P and a correspondingly lower proportion of P sorbed to calcite (CaCO 3 ) than unamended and gypsum‐amended soils. Backscattered electron imaging of SEM‐EDX revealed that alum‐ and Epsom salt‐amended treatments had P‐enriched microsites frequently associated with aluminum (Al), iron (Fe), magnesium (Mg), and calcium (Ca), which was not observed in other treatments. Induced precipitation of apatite‐like species may have been responsible for reduced P loss to snowmelt previously reported with fall application of amendments.