The Acid-Base Buffer Capacity of Red Soil Variable Charge Minerals and Its Surface Complexation Model

doi:10.6023/A17020056

Acta Chim. Sinica ›› 2017, Vol. 75 ›› Issue (6): 637-644.DOI: 10.6023/A17020056 Previous Articles

Special Issue: 铁环境化学

Article

红壤可变电荷矿物的酸碱缓冲能力及表面络合模型

程鹏飞^a,b, 王莹^b, 程宽^b, 李芳柏^b, 秦好丽^a, 刘同旭^b

a 贵州师范大学化学与材料科学学院贵阳 550001;
b 广东省生态环境技术研究所广东省农业环境综合治理重点实验室广州 510650

投稿日期:2017-02-15 发布日期:2017-04-25
通讯作者: 刘同旭 E-mail:txliu@soil.gd.cn
基金资助:
项目受科技部红壤酸化973项目（2014CB441002）和国家自然科学基金委中英国际合作红壤关键带项目（41571130052）资助.

The Acid-Base Buffer Capacity of Red Soil Variable Charge Minerals and Its Surface Complexation Model

Cheng Pengfei^a,b, Wang Ying^b, Cheng Kuan^b, Li Fangbai^b, Qin Haoli^a, Liu Tongxu^b

a School of Chemistry and Materials Science, Guizhou Normal University, Guiyang 550001, China;
b Guangdong Institute of Eco-environmental Science & Technology, Guangdong Key Laboratory of Integrated Agro-environmental Pollution Control and Management, Guangzhou 510650, China

Received:2017-02-15 Published:2017-04-25
Contact: 10.6023/A17020056 E-mail:txliu@soil.gd.cn
Supported by:
Project supported by the "973" Program (2014CB441002) and the National Natural Science Foundation of China (41571130052).

Iron oxides and kaolinite are the main sources of variable charges in the red soil. As a result of being protonated and deprotonated under different acid-base conditions, the surface hydroxyl groups can buffer the pH changes of red soil. In this study, iron oxide and kaolinite were titrated by the standard HCl and NaOH solution through the auto potentiometric titration under the controlled pH=2.9~9.5, to study the surface charge of soil minerals. The X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and N₂ desorption/adsorption isotherms (BET) were used to characterize the crystal structures, surface groups and specific surface areas of soil minerals. Based on the characterization data and titration curves, the acid-base properties of the minerals were analyzed by using 1-site/2-pK surface complexation model. The Gran plot method, commonly used to determine the equivalence points, was applied to calculate the concentration (H_s) and density (D_s) of the surface active sites on the soil minerals. The acid-base equilibrium constants (pK_a^int) of soil minerals were obtained by extrapolation and the corresponding pH_pzc were calculated by the following formula:pH_pzc=1/2 (pK_a1^int+pK_a2^int). The result of calculated value of pH_pzc was nearly equal with the experimental value, which showed that it is feasible to apply this model calculation method on the soil minerals. In addition, the above parameters can explain the acid-base buffer capacity of the minerals quantitatively. The results show that goethite and kaolinite have the higher surface active site concentration. According to the parameters, the surface chemical speciation of minerals at different pH were calculated by Visual Minteq software with the double layer model (DLM) to explain the mechanism of acid-base buffer behavior on the mineral surfaces. Finally, the acid-base titration method and model calculation approach were also used to analyze the acid-base buffer capacity of the natural red soil samples. The feasibility of this method on the red soil was further verified. Then, the surface chemical species (≡SOH₂⁺, ≡SO^- and ≡SOH) of the red soil were calculated by surface complex model to further explain their acid-base buffer mechanism.

Key words: iron oxide, kaolinite, red soil, acid-base buffer capacity, surface complexation model

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Cheng Pengfei, Wang Ying, Cheng Kuan, Li Fangbai, Qin Haoli, Liu Tongxu. The Acid-Base Buffer Capacity of Red Soil Variable Charge Minerals and Its Surface Complexation Model[J]. Acta Chim. Sinica, 2017, 75(6): 637-644.

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红壤可变电荷矿物的酸碱缓冲能力及表面络合模型

The Acid-Base Buffer Capacity of Red Soil Variable Charge Minerals and Its Surface Complexation Model

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