硅钙基材料的制备及其对镉污染土壤钝化效果研究

doi:10.16258/j.cnki.1674-5906.2025.08.013

生态环境学报 ›› 2025, Vol. 34 ›› Issue (8): 1282-1292.DOI: 10.16258/j.cnki.1674-5906.2025.08.013

• 研究论文【环境科学】 • 上一篇下一篇

硅钙基材料的制备及其对镉污染土壤钝化效果研究

林嘉茵¹^,²(), 侯玉婷¹^,², 曾海岑¹^,², 李伟志⁵, 李冬琴⁴, 叶挺进³, 陈火君¹^,²^,^*()

1.华南农业大学资源环境学院/农业农村部华南耕地保育重点实验室，广东广州 510642
2.华南农业大学资源环境学院/广东省农业资源利用重点实验室，广东广州 510642
3.佛山市铁人环保科技有限公司，广东佛山 528000
4.广东省农业科学院农业质量标准与监测技术研究所，广东广州 510640
5.紫金县农业综合服务中心，广东河源 517400

收稿日期:2024-12-05 出版日期:2025-08-18 发布日期:2025-08-01
通讯作者: *E-mail: hjchen@scau.edu.cn
作者简介:林嘉茵（2000年生），女，硕士研究生，从事农业面源、重金属防控污染和绿色投入品研究。E-mail: ljylf0723@163.com
基金资助:
国家重点研发计划项目(2022YFD1700804);广州市科技计划项目(2024A04J3256)

Preparation of Silicon-calcium-based Materials and Their Passivation Effects on Cadmium Contaminated Soil

LIN Jiayin¹^,²(), HOU Yuting¹^,², ZENG Haicen¹^,², LI Weizhi⁵, LI Dongqin⁴, YE Tingjin³, CHEN Huojun¹^,²^,^*()

1. Key Laboratory of Arable Land Conservation (South China), MOA/College of Natural Resources and Environment, South China Agricultural University, Guangzhou 510642, P. R. China
2. Guangdong Province Key Laboratory for Agricultural Resources Utilization/College of Natural Resources and Environment, South China Agricultural University, Guangzhou 510642, P. R. China
3. Foshan Tieren Environmental Protection Technology Co., Ltd., Foshan 528000, P. R. China
4. Institute of Quality Standard and Monitoring Technology for Agro-Products, Guangdong Academy of Agricultural Sciences, Guangzhou 510640, P. R. China
5. Zijin County Comprehensive Agricultural Service Center, Heyuan 517400, P. R. China

Received:2024-12-05 Online:2025-08-18 Published:2025-08-01

摘要/Abstract

摘要：

原位钝化技术作为一种简洁高效的土壤重金属化学修复手段，被广泛认为是实现镉污染农田安全生产的重要技术途径。为寻求高效经济的镉污染土壤钝化材料，以不同比例尾矿与石灰石进行混合，通过高温煅烧制备出粉末状（Calcium Silicate Powder，CSP）和球形（Calcium Silicate Sphere，CSS）硅钙基钝化材料。采用柠檬酸浸提缓释法研究两种硅钙基材料有效硅的释放特性，并通过土壤厌氧-好氧培养试验，评估不同形状硅钙基材料及其投加量对土壤中镉有效性的影响。结果表明，制备的CSP有效硅含量达20.3%，二氧化硅的活化率显著提高至60.8%，显著高于单一尾矿粉或石灰石粉。两种材料相比，CSS的初期溶出率为2.6%，表现出良好的缓释特性。两种硅钙基材料的施用显著提高了土壤pH值，降低了孔隙水中亚铁离子浓度，进而有效减少了土壤中镉的有效性。当两种材料的投加量为0.8%时，与对照组（不添加钝化材料）相比，CSP和CSS使土壤水溶态镉含量分别降低90.2%和61.4%，CaCl₂提取态镉分别降低42.4%和24.3%，且土壤中可交换态镉显著转化为残渣态镉，其中添加0.8%CSP的效果最佳，可交换态镉降低了15.6%。综上，两种硅钙基材料均能显著提高土壤pH及有效硅含量，CSS相比CSP具有更显著的缓释特性，而CSP因比表面积大、吸附能力强，在降低土壤镉有效性方面效果更为优异，在镉污染土壤修复中具有重要应用潜力。

关键词: 硅钙基材料, 镉, 缓释特性, 土壤钝化, 水稻土, 修复

Abstract:

In situ immobilization, as a simple and efficient chemical remediation method for soil heavy metals, is widely recognized as an important strategy for ensuring safe production of cadmium (Cd)-contaminated farmlands. To identify efficient and economical immobilizers for Cd-contaminated soils, mine tailings and limestone were mixed at different ratios and calcined under various high-temperature conditions. These processes yielded two types of immobilizers: Calcium Silicate Powder (CSP) and Calcium Silicate Sphere (CSS). The optimal preparation conditions were determined, and the characteristics of the silicon released were investigated using citric acid leaching. Through anaerobic-aerobic soil incubation experiments, the impacts of the immobilizer types and their application rates on Cd availability in soil were evaluated. The results showed that CSP contained 20.3% available silicon, with a silica activation percentage of 60.8%, which was significantly higher than that of the individual tailings or limestone powders. Compared to CSP, CSS had a lower initial dissolution percentage of 2.6%, indicating stronger slow-release properties. Both immobilizers significantly increased soil pH and reduced ferrous ion concentrations in pore water, thereby effectively lowering Cd availability in the soil. At an application rate of 0.8% of the soil mass, CSP and CSS reduced the water-soluble Cd content in the soil by 90.2% and 61.4%, respectively, and Cd extracted by calcium chloride decreased by 42.4% and 24.3%, respectively, compared to the control without an immobilizer. Moreover, exchangeable Cd in the soil was significantly reduced by 15.6% with 0.8% CSP application and was converted to the residual fraction. In summary, both calcium silicate-based immobilizers significantly increased the soil pH and available silicon content. While CSS demonstrates a stronger slow-release capacity, CSP exhibits exceptional efficacy in reducing the availability of Cd in soil owing to its extensive specific surface area and robust adsorption capability. These findings highlight the potential of CSP and CSS to remediate Cd-contaminated soil.

Key words: calcium silicate-based material, cadmium, slow-release property, soil passivation, paddy soil, remediation

中图分类号:

林嘉茵, 侯玉婷, 曾海岑, 李伟志, 李冬琴, 叶挺进, 陈火君. 硅钙基材料的制备及其对镉污染土壤钝化效果研究[J]. 生态环境学报, 2025, 34(8): 1282-1292.

LIN Jiayin, HOU Yuting, ZENG Haicen, LI Weizhi, LI Dongqin, YE Tingjin, CHEN Huojun. Preparation of Silicon-calcium-based Materials and Their Passivation Effects on Cadmium Contaminated Soil[J]. Ecology and Environmental Sciences, 2025, 34(8): 1282-1292.

图/表 12

图1 球形硅钙基钝化材料（CSS）与粉末状硅钙基钝化材料（CSP）样品图

Figure 1 Sample diagram of sphere calcium silicate-based passivation material (CSS) and powdered calcium silicate-based passivation material (CSP)

表1 材料的基本氧化物模式组成

Table 1 Basic oxide mode composition of materials %

材料类型	w_(SiO2)/%	w_(CaO)/%	w_(Al2O3)/%	w_(Fe2O3)/%	w_(MgO)/%	w_(K2O)/%
尾矿粉	83.18	3.38	6.37	0.69	0.35	1.88
石灰石粉	7.09	80.76	1.82	12.70	8.11	0.56

表2 供试材料各重金属总质量分数

Table 2 Total content of each heavy metal in the test materials

材料类型	w_(Cd)/ (mg·kg⁻¹)	w_(As)/ (mg·kg⁻¹)	w_(Cr)/ (mg·kg⁻¹)	w_(Pd)/ (mg·kg⁻¹)
尾矿粉	0.18	6.27	40.35	14.21
石灰石粉	－	2.12	35.32	17.53
土壤调理剂通用要求（NY/T 3034—2016）	10	10	50	50

图2 原材料及硅钙基材料的XRD图谱

Figure 2 XRD patterns of limestone powder, tailings powder and calcium silicate-based material

图3 材料样品同步热分析TG-DTG曲线及差热曲线

Figure 3 Simultaneous thermal analysis of material samples TG-DTG curve and differential thermal curve

图4 温度及石灰石对有效硅质量分数的影响

Figure 4 The effect of temperature and limestone content on the content of available silicon

图5 硅钙基材料7 d静置pH变化及有效硅溶出曲线

Figure 5 7-day static pH change of silica-calcium based materials and effective silicon dissolution curve

表3 硅钙基材料的初期溶出率（Sin）和微分溶出率（Sd）

Table 3 Initial dissolution percentage (Sin) and differential dissolution percentage (Sd) of silica-calcium based materials

硅钙基材料	有效硅释放率/%							S_in/ %	S_d/ %
硅钙基材料	1 d	2 d	3 d	4 d	5 d	6 d	7 d	S_in/ %	S_d/ %
CSS	2.622	5.170	1.234	2.202	3.066	2.103	2.488	2.622	2.711
CSP	14.701	10.538	12.493	7.951	4.943	2.965	1.437	14.701	6.725

图6 不同处理土壤中pH、Eh及悬浊液中亚铁、水溶态硅质量分数的变化曲线

Figure 6 Variation curves of pH, Eh and Fe(H2O) (Ⅱ) and water soluble silicon in the suspensions of different treated soils

图7 24 d培养后不同处理土壤中有效硅质量分数

Figure 7 Effective silicon content in soil of different treatments after 24 days incubation

图8 不同处理水溶态镉及CaCl2提取态镉质量分数的变化曲线

Figure 8 Variation curves of water soluble cadmium and cadmium in CaCl2 extracted state content in different treatments

图9 不同处理镉形态分布占比

Figure 9 Percentage distribution of cadmium forms in different treatments

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硅钙基材料的制备及其对镉污染土壤钝化效果研究

Preparation of Silicon-calcium-based Materials and Their Passivation Effects on Cadmium Contaminated Soil

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