Effect of immobilizing reagents on soil Cd and Pb lability under freeze-thaw cycles: Implications for sustainable agricultural management in seasonally frozen land.

Agricultural soil contamination in seasonally frozen land threatens food security. It is necessary to investigate the effects of freeze-thaw cycles on heavy metal bioavailability so as to select suitable immobilization agents. In this study, the soil was collected from a mid-latitude agricultural site in Liaoning Province, China, which was spiked with cadmium (Cd) and lead (Pb). Four immobilization treatments were set up, including (i) corn stover biochar, (ii) organic fertilizer, (iii) combined biochar and organic fertilizer, and (iv) the control group. The immobilized soils were subjected to 16 freeze-thaw cycles to temperatures of -10 °C, -20 °C, and -30 °C. It was found that freeze-thaw cycling increased the labile cadmium (Cd) and lead (Pb) content in the soil (i.e., exchangeable). The organic fertilizer treatment performed best in short-term immobilization, which was demonstrated by the amount of diethylenetriaminepentaacetic acid (DTPA) extractable lead (Pb) being 17.3-53.3% lower than that of the other treatments, and 7.2-31.5% lower for cadmium (Cd). Biochar, on the other hand, displayed better long-term performance under freeze-thaw cycling. This is probably because the biochar's organic carbon content is relatively stable, and therefore, releases relatively little dissolved organic carbon (DOC) which could re-mobilize heavy metals. Furthermore, additional sorption sites are formed and the abundance of oxygen-containing functional groups increased when biochar breaks down during freeze-thaw cycles. Overall, the joint application of biochar and organic fertilizer had the greatest immobilization effect, which inhibited the cracking of soil aggregates, reduced the labile metal content, and displayed both short- and long-term immobilization effectiveness. It is suggested that combined biochar and organic fertilizer may offer an effective strategy for the sustainable agricultural management of cadmium (Cd) and lead (Pb) contaminated in seasonally frozen land.