Changes in solubility and chemical speciation of potassium, calcium, and silicon in wood ash by acid treatment

ABSTRACT This study investigated the relationship between the solubility and the chemical speciation of plant nutritional elements (K, Ca, and Si) in wood ash treated with a dilute solution of sulfuric acid or phosphoric acid. The diluted acid solutions were added to fly ash (FA) collected from a power plant, and the untreated and acid-treated FAs were analyzed for their contents of K, Ca, and Si. The crystalline phases of the untreated and acid-treated FAs were identified using X-ray diffraction (XRD), and the Si species were determined using X-ray absorption near-edge structure (XANES) spectroscopy. Sulfuric acid and phosphoric acid treatments did not affect the solubility of K in FA. Water soluble and citrate soluble K in FA were decreased by the addition of these acids. The water soluble Ca content in FA treated with phosphoric acid did not show a significant change compared to that in the untreated FA, but it increased up to 65 times in FA treated with sulfuric acid. It is suggested that CaCO3, which was the main Ca species in the untreated FA, was transformed into syngenite and gypsum by the sulfuric acid treatment. Hydrochloric acid soluble Si in the acid-treated FA decreased compared to that in the untreated FA. In contrast, the NaOH-soluble Si fraction, a method for selectively extracting silica gel, increased especially in the phosphoric acid-treated FA. The results of XANES analysis showed that the FA samples treated with 10–30% sulfuric acid or 10–30% phosphoric acid had a lower degree of Si polymerization than the untreated FA, which corresponded generally to the increased Si solubility in FAs. However, FA treated with 30% sulfuric acid had lower soluble Si despite a lower degree of polymerization than FA, which was attributed to a lower pH. These results suggest that the change in solubility of Si in the acid-treated FA was influenced by the degree of polymerization and the decrease in pH. From the viewpoint of a fertilizer use of FA, sulfuric acid-treated ash, which consists of both water soluble Ca and citrate soluble Ca, is suitable for Ca fertilizer, and phosphoric acid-treated ash, which has high NaOH-soluble Si, is suitable for Si fertilizer