Sorption of Cu by organic matter from the decomposition of rice straw

Abstract

Sorption of heavy metals on soil components plays an important role in reducing their mobility and bioavailability. Organic matter is an important sorbent of heavy metals in soil. Crop residues which are important sources of soil organic matter will undergo decomposition after addition to the soil. However, few studies reported the effect of organic matter decomposition on heavy metal sorption. This study aimed to investigate the effect of straw decomposition on the sorption of Cu. Rice straw was decomposed in aerobic conditions for 1, 3, 6, and 12 months, respectively. Solid organic matter in decomposed rice straw was collected and marked OM-1, OM-3, OM-6, and OM-12, respectively. Sorption isotherms and kinetics of Cu on solid organic matter were studied by batch experiments. The sorption of Cu was calculated by the difference between the amount of Cu added initially and that remained in the supernatant. Sorption thermodynamics of Cu were studied by isothermal titration calorimetry technique. Potential mechanisms of Cu sorption were analyzed by combining the information from sorption thermodynamics, desorption experiments, and Fourier transform infrared spectroscopy observations. All sorption experiments were carried out at pH 5.0. The maximum sorption of Cu was 165.8, 170.5, 186.6, and 226.9 mmol kg−1, and the rate constant of Cu sorption was 0.80, 0.58, 0.50, and 0.32 kg mmol−1 h−1 on OM-1, OM-3, OM-6, and OM-12, respectively, indicating that the maximum sorption of Cu increased while sorption rate of Cu decreased with increasing the duration of straw decomposition from 1 to 12 months. The negative values of Gibbs free energy change and positive values of enthalpy change and entropy change revealed that Cu sorption was spontaneous, endothermic in nature, and the randomness was increased during sorption. Carboxyl and hydroxyl in solid organic matter were involved in Cu sorption. The percentage of Cu desorbed by NH4Ac from OM-1, OM-3, OM-6, and OM-12 was 45.0, 43.5, 42.8, and 37.8 %, respectively. In the current study, the decomposition of straw promoted the sorption capacity but reduced the sorption rate of Cu on solid organic matter. Copper sorption was an endothermic and spontaneous process. The formation of inner-sphere complexes was the main mechanism of Cu sorption, and its role in Cu sorption tended to increase with increasing the duration of straw decomposition. The information will facilitate the understanding of the contamination and remediation of heavy metal in cropland.