Optimizing Oxalic Acid Application Regime to Maximize Sunflower Remediation Efficacy in Cd-Contaminated Soils

The exogenous application of oxalic acid is a potential approach to amplifying phytoremediation performance on Cd-contaminated soils. However, few studies explore the optimal oxalic acid application regime from a perspective of coupling different concentrations and timings to maximize Cd removal rate. Given this, a pot experiment was conducted using oil sunflower (Helianthus annuus L.) as the test plant. Oxalic acid was added to the pots at concentrations of 1, 2, 3, 4, 5, and 6 mmol/kg at 20, 30, 40, and 50 days after emergence. A control (CK) without exogenous oxalic acid was also included. We examined the discrepancies in various soil Cd forms, sunflower height, plant non-protein thiol (NPT) levels, and soil Cd remediation efficiency under different oxalic acid application regimes. The results showed that applying oxalic acid at a concentration of 4 mmol/kg reduced the proportion of Fe-Mn oxide Cd and organic Cd compared to the control (CK), while increased the proportion of available Cd. The optimal application time is 30 or 40 days after emergence. The addition of exogenous oxalic acid promoted the growth of sunflowers, with the greatest increase in plant height observed when 4 mmol/kg oxalic acid was applied at 30 days after emergence. Exogenous oxalic acid enhanced the absorption of Cd by sunflower roots, with the total Cd accumulation in roots, stems, and leaves being higher than in the control (CK). When 4 mmol/kg oxalic acid was applied at 30 days after emergence, the total Cd accumulation in roots, stems, and leaves was highest. Under different application times and concentration levels of oxalic acid, Cd accumulation was highest in roots, followed by leaves, with stems showing the lowest accumulation. The NPT content in each part is as follows: root > stem > leaf. Applying 5 mmol/kg oxalic acid after 30 days of sunflower emergence resulted in relatively higher total NPT content in roots, stems, and leaves compared to the control (CK). The TOPSIS model was used for comprehensive evaluation, which showed that 4 mmol/kg oxalic acid application at 30 days after emergence could be used as the optimal oxalic acid application regime for phytoremediation. These findings indicate that the addition of oxalic acid effectively promoted the absorption of Cd by sunflower and increased the efficiency of Cd removal from the rhizosphere soil, with the optimal removal of soil Cd achieved by applying oxalic acid at a concentration of 4 mmol/kg 30 days after the emergence of oilseed sunflower seedlings.