The isotopic exchange kinetic (IEK) method allows assessing the rate of orthophosphate ions (Pi) exchange between the solid phase and the solution of the soil with time. However, two challenges have to be tackled when using this technique in soils with a very low water extractable Pi concentration (CP) and with a high sorbing capacity for Pi. The first is that current colorimetric methods do not allow quantifying Pi concentrations lower than 10 ?g P L?1. While the second challenge is that a significant fractionation between P isotopes may occur in the soil solution system in the presence of soils with high Pi sorption capacity. We assessed here: i) whether concentrating the blue phosphomolybdate complex (BPMC) in hexanol prior to its measurement would allow to lower the detection and quantification limits of Pi, ii) whether a significant isotopic fractionation between 32Pi and 33Pi could occur during IEK experiments conducted in the presence of high Pi sorbing substrates (e.g., pure goethite or Malagasy soils) and iii) whether the IEK method when used in conjunction with the hexanol concentration of the BPMC to measure CP would detect changes in Pi isotopic exchangeability in a ferralsol cropped with upland rice following the input of manure or water soluble fertilizer. The detection and quantification limits of the BPMC concentrated by hexanol were 0.3 and 0.8 ?g P L?1, respectively, using a cell of 10 cm length for the colorimetric measurement. The IEK conducted on Pi amended goethite and on Malagasy soils with 32Pi and 33Pi did not show any systematic isotopic fractionation between both isotopes, suggesting that in these soils 31Pi and 32Pi or 33Pi have a similar behavior during isotopic exchange. The analysis of the soils sampled in the field experiment showed a significant increase in the amount of Pi isotopically exchangeable after 1 min only after the application of water soluble P. This increase was paralleled by increases in rice yield and P export by grain