Enhancing soil redox dynamics: Comparative effects of Fe-modified biochar (N-Fe and S-Fe) on Fe oxide transformation and Cd immobilization.

Biochar and modified biochar have gained wide attention for Cd-contaminated soil remediation. This study investigates the effects of rape straw biochar (RSB), sulfur-iron modified biochar (S-FeBC), and nitrogen-iron modified biochar (N-FeBC) on soil Fe oxide transformation and Cd immobilization. The mediated electrochemical analysis results showed that Fe modification effectively enhanced the electron exchange capacity (EEC) of biochar. After 40 days of anaerobic incubation, compared to the treatment without biochar (CK), the concentrations of CaCl2-extractable Cd in N-FeBC, S-FeBC, and RSB treatments decreased by 79%, 53%, and 23%, respectively. Compared with S-FeBC, N-FeBC significantly decreased the soil Eh and increased soil pH within the first 15 days, which could be attributed to its higher EEC and alkalinity. There is a negative correlation between the concentration of CaCl2-extractable Cd and soil pH (p < 0.01). The sequential extraction results showed that both N-FeBC and S-FeBC promoted Cd transfer from acid-soluble to Fe/Mn oxides bound fraction (Fe/Mn-Cd). N-FeBC significantly increased the concentration of amorphous Fe oxides (amFeox) from 4.0 g kg-1 in day 1 to 4.6 g kg-1 in day 15 by promoting the NO3--reducing Fe(II) oxidation process, while S-FeBC significantly increased amFeox from 4.0 g kg-1 in day 15 to 4.8 g kg-1 in day 40 by promoting the Fe(II) recrystallization. There is a positive correlation between the concentration of amFeox and Fe/Mn-Cd (p < 0.01). The scanning electron microscopy analysis showed that Cd was bound to the amFeox coating on the surface of Fe-modified biochar. By acting as an electron shuttle, the active surface of Fe-modified biochar may serve as a hotspot for Fe transformation, which promotes amFeox formation and Cd immobilization. This study highlights the potential of Fe-modified biochar for the remediation of Cd-contaminated soils and provides valuable insights into the development of effective remediation approaches for Cd-contaminated soils.

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 (Fed) 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 Fed showed that Fe2+ promoted the reformatted of seconded Fe minerals after Day 12, and the Fed in the HB2 treatments increased by 31.5% in this period. RSB addition also promoted the reformation of poorly crystallized Fe oxide (Feo) 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 SO42- 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.

Biochar decreases Cd mobility and rice (Oryza sativa L.) uptake by affecting soil iron and sulfur cycling.

Biochar has been used as an amendment in Cd-contaminated soils. However, the mechanisms of which biochar reduce Cd mobility and rice (Oryza sativa L.) Cd uptake by modifying the iron and sulfur cycling in soil has rarely been addressed in the literature. A pot experiment has been carried out with two Cd-contaminated paddy soils (FG and DBS) from South China. Rice straw biochar (RSB) and rape straw biochar (RASB) pyrolyzed at 450 °C were applied at 0, 0.5, and 1% (w/w), respectively. The results showed that biochar amendment at a rate of 1% reduced grain Cd concentrations by 29.3-35.2%. Furthermore, biochar significantly reduced the Cd concentration of root, while the decline of Cd concentration by RASB treatment was higher than by RSB treatment. Root Cd in RASB0.5 was significantly reduced by 56.4-51.8% compared to than that in RSB0.5 at the maturing stage. Biochar reduced soil acid-soluble Cd by 15.9-25.3% with the increase of pH at the maturing stage in FG soil, and 30.1-59.3% by promoting soil into more reductive condition at the heading stage in DBS soil with higher contents of Fe and S. In addition, biochar impeded Cd transport from soil to rice roots by increasing the formation of iron plaque at the flooding stage. Owing to the influence of RASB1, DCB-Cd concentration increased significantly, with 99.7% at the heading stage in FG soil and 237.9% at the tillering stage in DBS soil, respectively. Furthermore, RASB with a higher sulfur concentration had a more positive effect on Cd immobilization and iron plaque formation compared to RSB. As a conclusion, this study suggested that biochar might be able to promote the Cd immobilization by affecting the cycling of iron and sulfur in soil.