Sun Qi, Wu Ji-Zi, Wu Qiu-Chan, Lian Bin, Yuan Feng, Zhao Ke-Li
College of Environmental and Resources Sciences, College of Carbon Neutrality, Zhejiang A&F University, Hangzhou 311300, China.
Key Laboratory of Soil Contamination Bioremediation of Zhejiang Province, Zhejiang A&F University, Hangzhou 311300, China.
Huan Jing Ke Xue. 2024 Nov 8;45(11):6677-6688. doi: 10.13227/j.hjkx.202311127.
Due to the aggravation of atmospheric nitrogen and sulfur deposition and the unreasonable application of fertilizer, soil acidification is becoming increasingly serious. In heavy metal-contaminated soils, acidification not only seriously affects fertility but also the effectiveness and sustainability of conventional passivation remediation materials such as biochar. The application of calcium fertilizer may improve soil acidification, alleviate the aging of biochar materials in soil, and improve its remediation ability to composite polluted soil. However, the mechanism of its effect is still unclear. Based on this, this study selected iron-manganese oxide (FM) and hickory cattails biochar (BC) to prepare biochar-ferromanganese composites (BFM) and conducted simulated acidification on it. Through characterization and an aqueous adsorption test, the changes in physicochemical properties and adsorption properties of the material after acidification were explored. Then, orthogonal tests were carried out to explore the effects of the combination of BFM and calcium fertilizer on soil pH and the availability of Cd and As under acidification conditions and to obtain the best combination scheme. The results showed that the optimal ratio of BC and FM in BFM was 7∶3 (quality ratio), the removal rates of Cd(Ⅱ) and As(Ⅲ) were as high as 94.58% and 97.14%, respectively, and the adsorption capacities were 120.74 mg·g and 129.29 mg·g (solid-liquid ratio 1∶500). After acidification treatment, the pore structure of BFM surface decreased, and the types and quantities of functional groups changed, resulting in the removal rates of Cd(Ⅱ) and As(Ⅲ) in aqueous solution decreasing by 73.97%-92.84% and 73.56%-93.61%, respectively. The combined application of calcium fertilizer and BFM could significantly increase soil pH, with an increase range of 3.06%-37.84%. The effect of increasing pH decreased with the increase in culture time and acidification degree. Compared with that in the blank control, the content of available Cd in soil was significantly reduced by 22.67%-97.78%. The content of available As in soil was generally stable. According to the effect curve analysis of the orthogonal test results, under the condition of weak acidification degree (pH=5.6), the application of 2% supplemental amount with 2% silica-calcium fertilizer and 2% calcium-magnesium phosphate fertilizer had a good passivation effect on soil Cd. Under the condition of strong acidification degree (pH=4.0), the application of 2% supplemental amount and 2% silica-calcium fertilizer had a good passivation effect on soil As. In summary, simulated acidification will affect the adsorption performance of BFM, and calcium fertilizer combined with it can increase soil pH, improve soil acidification, alleviate the aging of BFM in acidified soil, and improve its repair ability to heavy metal-polluted soil.
由于大气氮硫沉降加剧以及肥料施用不合理,土壤酸化问题日益严重。在重金属污染土壤中,酸化不仅严重影响土壤肥力,还影响生物炭等传统钝化修复材料的有效性和可持续性。施用钙肥可能改善土壤酸化状况,缓解生物炭材料在土壤中的老化现象,并提高其对复合污染土壤的修复能力。然而,其作用机制尚不清楚。基于此,本研究选用铁锰氧化物(FM)和香蒲生物炭(BC)制备生物炭 - 铁锰复合材料(BFM),并对其进行模拟酸化。通过表征和水相吸附试验,探究了酸化后材料理化性质和吸附性能的变化。然后进行正交试验,探究BFM与钙肥组合在酸化条件下对土壤pH值以及镉和砷有效性的影响,从而得出最佳组合方案。结果表明,BFM中BC与FM的最佳比例为7∶3(质量比),对Cd(Ⅱ)和As(Ⅲ)的去除率分别高达94.58%和97.14%,吸附容量分别为120.74 mg·g和129.29 mg·g(固液比1∶500)。酸化处理后,BFM表面孔隙结构减少,官能团种类和数量发生变化,导致水溶液中Cd(Ⅱ)和As(Ⅲ)的去除率分别下降73.97% - 92.84%和73.56% - 93.61%。钙肥与BFM联合施用可显著提高土壤pH值,增幅为3.06% - 37.84%。随着培养时间和酸化程度的增加,pH值升高的效果逐渐减弱。与空白对照相比,土壤中有效态Cd含量显著降低22.67% - 97.78%。土壤中有效态As含量总体保持稳定。根据正交试验结果的效应曲线分析,在弱酸程度(pH = 5.6)条件下,施用2%添加量的硅钙肥和钙镁磷肥对土壤Cd具有良好的钝化效果。在强酸程度(pH = 4.0)条件下,施用2%添加量的硅钙肥对土壤As具有良好的钝化效果。综上所述,模拟酸化会影响BFM的吸附性能,钙肥与之配合可提高土壤pH值,改善土壤酸化状况,缓解BFM在酸化土壤中的老化现象,并提高其对重金属污染土壤的修复能力。