25 years of continuous sewage sludge application vs. mineral fertilizers on a calcareous soil affected pH but not soil carbonates

Inorganic and organic fertilizers have been widely used to maintain crop yields. However, several studies have demonstrated that the dissolution of carbonates in agricultural soils by the acidification induced by N-fertilizers can result in their total or partial loss in the tilled layer of some agricultural soils. The effect of inorganic and organic fertilization on carbonates in calcareous semiarid Mediterranean soils has been less studied and is still unclear. Based on a 25-year field experiment, we investigated the effects of different fertilization strategies on the soil pH, inorganic C content, and in the proportion of pedogenic carbonates in the topsoil (0-30 cm) of a carbonate-rich soil in Navarre (N Spain). Five treatments were compared: no amendments as a control (SC), mineral fertilization (MF), and the application of sewage sludge at different doses (80 Mg ha^-1 every year (80-1), 40 Mg ha^-1 every year (40-1) and 40 Mg ha^-1 every four years (40-4). Results showed a decrease in soil pH values by increasing the amount of sewage sludge and a small alteration in the calcite structure particularly in 40-4. However, no significant differences between treatments were found in the total content of carbonates nor in the proportion of pedogenic carbonates. The high concentration of total carbonates in the soil (16.09 ± 0.48%), and of the proportion of pedogenic carbonates (40.21 ± 1.29%, assuming a δ¹³C of primary carbonates = 0 ‰) seemed elevated enough to compensate for the observed acidification in the studied soil. In the case of MF, no changes were observed in the pH values, nor in the carbonate content (total and pedogenic). This suggests that the use of sewage sludge could induce changes in the future at a faster rate and of greater dimension than the use of mineral fertilizers such as the ones used in this field (46% urea, superphosphate and ClK).