Chemical speciation and release kinetics of Ni in a Ni-contaminated calcareous soil as affected by organic waste biochars and soil moisture regime

Biochars vary widely in properties and have been shown to have variable effects on potentially toxic element(s) stabilization in soil. This is the first study to examine the interaction effects of biochar and soil moisture regime on Ni stabilization in a Ni-contaminated calcareous soil. Three different organic waste (cow manure, municipal compost and licorice root pulp) biochars produced at two temperatures (300 and 600 degrees C) were applied (3% wt.) to a Ni-contaminated calcareous soil and incubated at field capacity and saturated conditions for 70 d. Sequential chemical fractionation and Ni release kinetics were then performed. All applied biochars, especially the high-temperature biochars, were significantly able to enhance Ni stabilization in the studied soil. In particular, the biochars significantly decreased Ni content in the water-soluble and exchangeable fractions (10-42% decrease), while increasing the immobile residual fraction (13-38% increase). The biochars also significantly decreased the rate and cumulative amount of EDTA-extractable Ni from the calcareous soil. Among the studied biochars, the cow manure and municipal compost biochars produced at 600 degrees C were the most effective at reducing Ni mobility factor (27-28% decrease) and initial release rate (42-49% decrease), likely due to their high ash content and pH, which promotes Ni sorption in soil. Soil moisture regime was not found to significantly affect the Ni mobility factor or rates of Ni release from the calcareous soil but did, however, affect certain soil Ni chemical fractions. Soil water saturation significantly decreased Ni in the Mn (4%) and non-crystalline Fe oxides (17%) fractions, while increased the crystalline Fe oxide fraction (3%), attributed to reductive dissolution of Mn and Fe oxide crystallinity enhancement. Saturation also significantly enhanced Ni in the residual fraction (4%), attributed to the associated pH increase and potential sulfide formation. The results of this study demonstrate that high temperature, ash-rich, and alkaline biochars are most effective at Ni immobilization, and that soil water saturation can further enhance Ni in the residual fraction.