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Abstract Efficient phosphorus (P) fertilization strategies are essential for intensive crop production with minimal negative environmental impacts. A key factor in sustainable P use is assessment of the plant available soil P pool using soil P tests. This study determined isotopically exchangeable P after six days of reaction with 33PO 4 (P- E (6 d)) to determine how accurately two commonly used P tests, Olsen and AL (acid ammonium acetate lactate) can quantify the amount of labile P. Soil samples were taken from both highly P-amended and unamended plots at six sites within the Swedish long-term soil fertility experiments. According to P K-edge XANES spectroscopy, the P speciation was dominated by Al-bound P and organic P, with additional contributions from Fe-bound P and Ca phosphates in most soils. The results showed that the AL test overestimated P- E (6 d) by a factor of 1.70 on average. In contrast, the Olsen test underestimated P- E (6 d), with the mean ratios of P-Olsen to P- E (6 d) being 0.52 for high-P and 0.19 for low-P soils. The 33P/31P ratio in the Olsen extract of a 33PO 4 spiked soil was closer to that of a 0.005 mol L−1 CaCl 2 soil extract than the corresponding ratio in the AL extract, suggesting that AL extraction solubilized more non-labile P. In conclusion, the AL and Olsen methods are not suitable for direct quantification of the isotopically exchangeable soil P pool after 6 days of equilibration. However, based on the results, Olsen may be superior to AL for classification of soil P status, due to its even performance for calcareous and non-calcareous soils and lower extraction of non-labile P. Highlights • Extraction with sodium bicarbonate (Olsen) underestimated isotopically exchangeable P. • P fertilization increased the ratio of Olsen-P to isotopically exchangeable P. • AL extraction solubilized a large fraction of non-isotopically exchangeable P. • For classification purposes, the Olsen test is probably superior to AL. [ABSTRACT FROM AUTHOR]

With time, different soil-forming processes such as weathering, plant growth, accumulation of organic matter, and cultivation are likely to affect phosphorus (P) speciation. In this study, the depth distribution of P species was investigated for an agricultural clay soil, Lanna, Sweden. Small amounts of apatite-P was demonstrated in the topsoil whereas the speciation of P at 70–100 cm depth consisted of approximately 86% apatite according to P K-edge XANES (X-ray absorption near-edge structure) spectroscopy. Because there were only minor differences in bulk mineralogy and texture, these variations in P speciation were interpreted as the result of apatite weathering of the topsoil. Speciation modeling on soil extracts supported this idea: hydroxyapatite was not thermodynamically stable in the top 50 cm of the soil. Apatite was enriched in the bulk soil relative to the clay fraction, as expected during apatite dissolution. Combined results from batch experiments, XANES spectroscopy and X-ray diffraction suggested chemical transformations of the topsoil as a result from accumulation of organic matter and airing from tillage followed by enhanced weathering of apatite, amphiboles, clay minerals, and iron oxides. This caused the formation of poorly crystalline secondary iron and aluminum (hydr)oxides in the topsoil, which retained part of the released P from apatite. Other P was incorporated into organic forms. Furthermore, the results also showed that short-term acidification below the current pH value (below 5.5 in the topsoil and 7.2 in the deeper subsoil) caused significant solubilization of P. This is attributed to two different mechanisms: the instability of Al-containing sorbents (e.g. Al hydroxides) at low pH (in the topsoil), and the acid-mediated dissolution of apatite (the subsoil). [ABSTRACT FROM AUTHOR]