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A common technique to quantitatively estimate P speciation in soil samples is to apply linear combination fitting (LCF) to normalized P K-edge X-ray absorption near-edge structure (XANES) spectra. Despite the rapid growth of such applications, the uncertainties of the fitted weights are still poorly known. Further, there are few reports to what extent the LCF standards represent unique end-members. Here, the co-variance between 34 standards was determined and their significance for LCF was discussed. We present a probabilistic approach for refining the calculation of LCF weights based on Latin hypercube sampling of normalized XANES spectra, where the contributions of energy calibration and normalization to fit uncertainty were considered. Many of the LCF standards, particularly within the same standard groups, were strongly correlated. This supports an approach in which the LCF standards are grouped. Moreover, adsorbed phytates and monetite were well described by other standards, which puts into question their use as end-members in LCF. Use of the probabilistic method resulted in uncertainties ranging from 2 to 11 percentage units. Uncertainties in the calibrated energy were important for the LCF weights, particularly for organic P, which changed with up to 2.7 percentage units per 0.01 eV error in energy. These results highlight the necessity of careful energy calibration and the use of frequent calibration checks. The probabilistic approach, in which at least 100 spectral variants are analyzed, improves our ability to identify the most likely P compounds present in a soil sample, and a procedure for this is suggested in the paper.

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To improve phosphorus (P) fertilization and environmental assessments, a better understanding of release kinetics of solid-phase P to soil solution is needed. In this study, Fe (hydr)oxide-coated filter papers (Fh papers), isotopic exchange kinetics (IEK) and chemical extractions were used to assess the sizes of fast and slowly desorbing P pools in the soils of six long-term Swedish field experiments. The P desorption data from the Fh-paper extraction of soil (20 days of continual P removal) were fitted with the Lookman two-compartment desorption model, which estimates the pools of fast (Q 1 ) and slowly (Q 2 ) desorbing P, and their desorption rates k 1 and k 2 . The amounts of isotope-exchangeable P (E) were calculated (E 1min to E >3 months ) and compared with Q 1 and Q 2 . The strongest relationship was found between E 1 min and Q 1 (r 2 = .87, p < .01). There was also an inverse relationship between the IEK parameter n (the rate of exchange) and k 1 (r 2 = .52, p < .01) and k 2 (r 2 = .52, p < .01), suggesting that a soil with a high value of n desorbs less P per time unit. The relationships between these results show that they deliver similar information, but both methods are hard to implement in routine analysis. However, Olsen-extractable P was similar in magnitude to Q 1 (P-Olsen = 1.1 × Q 1 + 2.3, r 2 = .96), n and k 1 were related to P-Olsen/P-CaCl 2 , while k 2 was related to P-oxalate/P-Olsen. Therefore, these extractions can be used to estimate the sizes and desorption rates of the different P pools, which could be important for assessments of plant availability and leaching.

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