Copper and Zn distribution in humic substances of soil after 10 years of pig manure application in south of Santa Catarina, Brazil

This study aims to evaluate available Cu and Zn levels in soil and related in soil organic matter (SOM) fractions (fulvic acids-FA, humic acids-HA, and humins-HU) after 10 years of application of pig slurry (PS) and pig deep litter (PL). Soil samples were collected from an experiment with black oat/corn succession under no-tillage in southern Brazil. The treatments consisted of fertilization of 90 and 180 kg N ha(-1) applied as PS and PL from 2002 to 2012 and a control treatment without any fertilization. SOM chemical fractionation was performed in air-dried samples. Copper and Zn concentrations were analyzed in soil (total, EDTA- and CaCl2-extracted) and in SOM fractions. The amount of Cu and Zn (in mol) related to each fraction of SOM (Cu/C and Zn/C molar ratios) was established. The applications of PS and PL promoted the accumulation of total and available Cu and Zn, especially in the PL180 treatment. The highest amount of Zn was found with HU, while for Cu both HA and HU were important retention compartments. The highest Cu/C-FA, Cu/C-HA and Cu/C-HU ratios were found with the addition of PL. Increases in Zn/C ratio were found mainly in FA fraction. The high levels of Cu and Zn obtained in the HCl-extracted SOM fraction suggest that a considerable part is bound to SOM and clay minerals with low energy. However, the SOM is an important source of metal adsorption in soils with swine manure application.