Rape straw biochar enhanced Cd immobilization in flooded paddy soil by promoting Fe and sulfur transformation

Cd is normally associated with sulfide and Fe oxides in flooded paddy soil. The mechanisms of biochar enhanced Cd immobilization by promoting Fe transformation and sulfide formation are unclear. Rape straw biochar (RSB) pyrolyzed at 450 °C (LB) and 800 °C (HB) was added to Cd-contaminated paddy soil at 1% (LB1, HB1) and 2% (LB2, HB2) doses. The results showed that Fe/Mn oxide-Cd (Fe/Mn-Cd) and free Fe oxide (Fe_d) concentrations decreased in the first 12 days and then rose, while Fe²⁺ in pore water (W-Fe²⁺) tended to rise first and then fall. The electron transfer rate of soil in the HB2 treatment was 4.9-fold higher than that in the treatment without biochar (CK). Fe oxide reduction was enhanced by RSB, with a maximum increase in W-Fe²⁺ by 62.1% in HB2 on Day 12. The negative correlation between W-Fe²⁺ and Fe_d showed that Fe²⁺ promoted the reformatted of seconded Fe minerals after Day 12, and the Fe_d in the HB2 treatments increased by 31.5% in this period. RSB addition also promoted the reformation of poorly crystallized Fe oxide (Fe_o) by increasing soil pH, which increased by 17.2% and 15.1% on average in the LB2 and HB2 treatments, respectively, compared to CK. Compared to Day 7, the increased rate of Fe/Mn-Cd on Day 30 in RSB was approximately twice that of CK. Compared to the molybdate group, the maximum decrease in CaCl₂-Cd was 29.1% in LB2 on Day 12. LB2 increased SO₄^2- and acid-volatile sulfide concentrations by 6.9- and 4.1-fold, respectively, compared to CK. These results suggested that RSB, particularly HB, promoted more Cd adsorption in Fe minerals by increasing Fe hydroxylation and recrystallization processes. LB increased the contribution of sulfide to Cd immobility.