Long-term manure application effects on phosphorus speciation, kinetics and distribution in highly weathered agricultural soils.

Phosphorus (P) K-edge XANES and Fe K-edge EXAFS spectroscopies along with sequential P chemical fractionation and desorption kinetics experiments, were employed to provide micro- and macro-scale information on the long-term fate of manure application on the solid-state speciation, kinetics and distribution of P in highly weathered agricultural soils of southern Brazil. Soil test P values ranged from 7.3 up to 16.5 times as much higher than the reference soil. A sharp increase in amorphous Fe and Al amounts were observed as an effect of the consecutive application of manures. Whereas our results showed that the P sorption capacity of some manured soils was not significantly affected, P risk assessment indices indicated that P losses should be expected, likely due to the excessive manure rates applied to the soils. The much higher contents of amorphous Fe and Al (hydr)oxides (55% and 80% increase with respect to the reference soil, respectively) in manured soils seem to have counterbalanced the inhibiting effect of soil organic matter on P sorption by creating additional P sorption sites. Accordingly, the newly created P sorbing surfaces were important to prevent an even larger P loss potential. Phosphorus K-edge XANES lent complimentary hints on the loss of crystallinity and transformation of originally present Fe-P minerals into poorly crystalline ones as an effect of manuring, whereas Fe K-edge EXAFS provided insights into the structural changes underwent in the soils upon manure application and soil management.