The use of low molecular weight organic acids (LMWOAs) for the phytoremediation of heavy metals has become a promising technique. We chose five kinds of organic acids (oxalic acid (OA), acetic acid (AA), tartaric acid (TA), malic acid (MA), and citric acid (CA)) with six application rates (1, 2, 3, 4, 5, and 6 mmol/kg) and planted sunflowers (Helianthus annuus L.) in Cd-polluted soil to study the efficiency of the phytoremediation of Cd and the degree of Cd toxicity to plants. Treatment with no acid application served as the control (CK). We analyzed the plant height dry matter and the Cd and nonprotein sulfhydryl (NPT) contents in the soil and plant tissues. OA, AA, TA, MA, and CA increased plant heights by 17.6–47.40%, 21.25–39.17%, 12.5–35.52, 5.10–30.50%, and 16.15–49.17%, respectively; shoot biomass of the sunflowers was increased except with MA. NPT decreased under LMWOA application, which, in the roots, increased with the increase in root Cd under LMWOA treatment; however, there was no obvious relationship in the stems and leaves. The composition of Cd in the soil changed significantly under the LMWOA treatments compared to the CK, and the changes in carbonate Cd and Fe-Mn oxide Cd were the most prominent. The plant Cd accumulation of OA, AA, TA, MA, and CA increased by 43.31%, 55.25%, 48.69%, 0.52%, and 32.94%, respectively, and the increase in root Cd content and shoot dry matter quality promoted the increase in Cd accumulation. The LMWOAs were more likely to affect the phytoremediation of Cd by changing total P (TP) rather than total N (TN).

Applying exogenous organic acids is an effective method to improve the remediation efficiency of Cd-contaminated soils. To investigate the effects of exogenous acetic acid on Cd forms in rhizosphere soils and phytoremediation performance for Cd-contaminated soils, a potted experiment was performed with oilseed sunflower as the extractive plant. Acetic acid was applied at 1, 2, 3, 4, 5, and 6 mmol/kg at 20, 30, 40, and 50 days after seedling emergence. Soil without acetic acid was used as a control (CK). Emblematic chemical properties and different Cd forms in rhizosphere soils were inspected. Results showed that adding acetic acids improved the biomass of shoot and root; it increased firstly and then decreased with the increase of acetic acid concentrations. For all treatments, acetic acids increased sucrase activity and catalase activity but decreased amylase activity in rhizosphere soils. At 30 or 40 days after seedling emergence, the exchangeable Cd content, Fe-Mn oxide Cd content, and organic Cd content were lower, while the carbonate Cd content was greater. Adding acetic acids improved the removal rate of Cd, and when 1 mmol/kg acetic acid was applied at 40 days after seedling emergence, it was increased by 60%, which was the highest compared to CK. RDA showed that catalase activity, sucrase activity, carbonate Cd, and pH could promote the growth of oilseed sunflower, while organic Cd, Fe-Mn oxide Cd, total Cd, exchangeable Cd, and amylase activity inhibited the growth of oilseed sunflower. These findings suggest that acetic acid can improve the efficiency of phytoremediation in Cd-contaminated soils. In particular, the treatment with 1 mmol/kg acetic acid at 40 days after seedling emergence had the most obvious effect.

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.