Citation: 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 Chimica Sinica, ;2017, 75(6): 637-644. doi: 10.6023/A17020056 shu

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

Corresponding author: Liu Tongxu, txliu@soil.gd.cn
Received Date: 15 February 2017

Fund Project: the "973" Program 2014CB441002the National Natural Science Foundation of China 41571130052

Figures(8)

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.
- iron oxide,
- kaolinite,
- red soil,
- acid-base buffer capacity,
- surface complexation model
1. [1]
  Li, Q. K. Chinese Red Soil, Vol. 1~2, Eds.:Zhao, Q. G.; Shi, H.; Gong, Z. T., Science Press, Beijing, 1983, p. 1(in Chinese).
2. [2]
  Xiong, Y.; Li, Q. K. Chinese Soil, Science Press, Beijing, 1990, pp. 502~508(in Chinese).
3. [3]
  Brown, K. A. Water, Air, Soil Pollut. 1987, 32, 201.
4. [4]
  Liao, B.; Guo, Z.; Zeng, Q.; Probst, A.; Probst, J. Water, Air, Soil Pollut.:Focus 2007, 7, 151. doi: 10.1007/s11267-006-9077-7
5. [5]
  Fu, L.; Wu, J.; Yang, Y.; Qiu, L. Environ. Sci. 1993, 14(1), 20(in Chinese).
6. [6]
  Zhao, Y.; Duan, L.; Xing, J.; Larssen, T.; Nielsen, C. P.; Hao, J. Environ. Sci. Technol. 2009, 43, 8021. doi: 10.1021/es901430n
7. [7]
  Guo, J. H.; Liu, X. J.; Zhang, Y.; Shen, J. L.; Han, W. X.; Zhang, W. F.; Christie, P.; Goulding, K. W. T.; Vitousek, P. M.; Zhang, F. S. Science 2010, 327, 1008. doi: 10.1126/science.1182570
8. [8]
  Liao, B. H.; Dai, Z. H. Acta Sci. Circumstantiae 1991, 11, 425(in Chinese).
9. [9]
  Reuss, J.; Cosby, B.; Wright, R. Nature 1987, 329, 27. doi: 10.1038/329027a0
10. [10]
  Wright, R.; Cosby, B.; Flaten, M.; Reuss, J. Nature 1990, 343, 53. doi: 10.1038/343053a0
11. [11]
  Larssen, T.; Schnoor, J. L.; Seip, H. M.; Dawei, Z. Sci. Total Environ. 2000, 246, 175. doi: 10.1016/S0048-9697(99)00457-X
12. [12]
  Li, J. Y.; Wang, N.; Xu, R. K. Soils 2009, 41, 932(in Chinese). doi: 10.3321/j.issn:0253-9829.2009.06.015
13. [13]
  Xu, R. K. Soils 2015, 47, 238(in Chinese).
14. [14]
  Alekseeva, T.; Alekseev, A.; Xu, R. K.; Zhao, A. Z.; Kalinin, P. Environ. Geochem. Health 2011, 33, 137. doi: 10.1007/s10653-010-9327-5
15. [15]
  Dixon, J. B.; Weed, S. B.; Dinauer, R. C. Minerals in Soil Environments, 2nd ed., Eds.:Barnhisel, R. I.; Bertsch, P. M., SSSA, USA, 1989, Chapter 15, p. 729.
16. [16]
  Yu, T. R.; Chen, Z. C. The Chemical Process in the Soil, Vol. 14, Ed.:Chen, Z. C., Science Press, Beijing, 1990, p. 432(in Chinese).
17. [17]
  Yu, T. R.; Wang, Z. Q. Soil Analytical Chemistry, Vol. 11, Eds.:Chen, J. F.; He, Q., Science Press, Beijing, 1987, p. 337(in Chinese).
18. [18]
  Wang, X. G.; Li, F. B. Persistent Organic Pollutants Forum and National Symposium on Persistent Organic Pollutants, Eds.:Yu, G.; Huang, J.; Wang, B.; Liu, Y. C., Chinese Chemical Society, Beijing, 2006, pp. 215~223(in Chinese).
19. [19]
  Wang, X. G.; Sun, L. R.; Zeng, F.; Li, F. B. Res. Environ. Sci. 2009, 22(4), 60(in Chinese).
20. [20]
  Gao, S.; He, G. P.; Wu, H. H.; Sun, W. Y. Acta Petrol. Mineral. 2005, 24, 239(in Chinese). doi: 10.3969/j.issn.1000-6524.2005.03.010
21. [21]
  Gao, Y.; Mucci, A. Geochim. Cosmochim. Acta 2001, 65, 2361. doi: 10.1016/S0016-7037(01)00589-0
22. [22]
  Tan, W. F; Zhou, S. Z.; Liu, F.; Feng, X. H.; Li, X. H. Soils 2007, 39(5), 726(in Chinese).
23. [23]
  Xu, R. K.; Zhao, A. Z.; Jiang, J. Ecol. Environ. 2011, 20(10), 1395 (in Chinese). doi: 10.3969/j.issn.1674-5906.2011.10.002
24. [24]
  Yu, X. J.; Chou, R. L. Chongqing Environ. Sci. 1998, 20(3), 11(in Chinese).
25. [25]
  Stumm, W. Chemistry of the Solid-water Interface:Processes at the Mineral-water and Particle-water Interface in Natural Systems, John Wiley & Son Inc., New York, 1992. pp. 13~23.
26. [26]
  Tombácz, E.; Szekeres, M. Langmuir 2001, 17, 1411. doi: 10.1021/la001322j
27. [27]
  Davis, J. A.; Leckie, J. O. J. Colloid Interface Sci. 1978, 67, 90. doi: 10.1016/0021-9797(78)90217-5
28. [28]
  Cagnasso, M.; Boero, V.; Franchini, M. A.; Chorover, J. Colloids Surf., B 2010, 76, 456. doi: 10.1016/j.colsurfb.2009.12.005
29. [29]
  Liu, T.; Li, X.; Li, F.; Zhang, W.; Chen, M.; Zhou, S. Colloids Surf., A 2011, 379(1), 143.
30. [30]
  Li, X.; Liu, T.; Li, F.; Zhang, W.; Zhou, S.; Li, Y. J. Soil. Sediment. 2012, 12(2), 217. doi: 10.1007/s11368-011-0433-5
31. [31]
  Zhou, D. H.; Li, X. H.; Xu, F. L. J. Huazhong Agric. Univ. 1996, 15(2), 153(in Chinese).
32. [32]
  Liu, T.; Li, X.; Li, F.; Tao, L.; Liu, H. Soil Sci. 2014, 179, 468. doi: 10.1097/SS.0000000000000092
33. [33]
  Djomgoue, P.; Njopwouo, D. J. Surf. Eng. Mater. Adv. Technol. 2013, 3, 275.
34. [34]
  Saikia, B. J.; Parthasarathy, G. J. Mod. Phys. 2010, 1, 206. doi: 10.4236/jmp.2010.14031
35. [35]
  Lu, S. J.; Tan, W. F.; Liu, F.; Feng, X. H. Acta Pedol. Sin. 2006, 43(5), 756(in Chinese).
36. [36]
  Szekeres, M.; Tombácz, E. Colloids Surf., A 2012, 414, 302. doi: 10.1016/j.colsurfa.2012.08.027
37. [37]
  Jolsterå, R.; Gunneriusson, L.; Forsling, W. J. Colloid Interface Sci. 2010, 342, 493. doi: 10.1016/j.jcis.2009.10.080
38. [38]
  Frini-Srasra, N.; Kriaa, A.; Srasra, E. Russ. J. Electrochem. 2007, 43, 795. doi: 10.1134/S1023193507070099
39. [39]
  Wu, Z. S.; Zhang, W. M.; Sun, Z. X. Acta Chim. Sinica 2010, 68(8), 769(in Chinese).
40. [40]
  Davis, J. A.; Kent, D. Rev. Mineral. Geochem. 1990, 23, 177.
41. [41]
  Kubicki, J. D.; Paul, K. W.; Kabalan, L.; Zhu, Q.; Mrozik, M. K.; Aryanpour, M.; Pierre-Louis, A. M.; Strongin, D. R. Langmuir 2012, 8, 14573.
42. [42]
  Cornell, R. M.; Schwertmann, U. The Iron Oxides:Structure, Properties, Reactions, Occurrences and Uses, John Wiley & Sons, 2003, pp. 221~223.
43. [43]
  Pagnanelli, F.; Bornoroni, L.; Toro, L. Environ. Sci. Technol. 2004, 38, 5443. doi: 10.1021/es049760q
44. [44]
  Liu, T.; Li, X.; Waite, T. D. Environ. Sci. Technol. 2014, 48, 14564. doi: 10.1021/es503777a
45. [45]
  Liu, T.; Li, X.; Waite, T. D. Environ. Sci. Technol. 2013, 47(13), 7350. doi: 10.1021/es400362w
46. [46]
  Liu, T.; Li, X.; Waite, T. D. Environ. Sci. Technol. 2013, 47(23), 13712. doi: 10.1021/es403709v
47. [47]
  Liu, T.; Li, X.; Zhang, W.; Hu, M.; Li, F. J. Colloid Interface Sci. 2014, 423, 25. doi: 10.1016/j.jcis.2014.02.026
48. [48]
  Yanina, S. V.; Rosso, K. M. Science 2008, 320(5873), 218. doi: 10.1126/science.1154833
49. [49]
  Janusz, W.; Skwarek, E.; Zarko, V. I.; Gun'ko, V. M. Physicochem. Probl. Miner. Process. 2007, 41, 215.
50. [50]
  Pyman, M.; Bowden, J.; Posner, A. Soil Res. 1979, 17, 191. doi: 10.1071/SR9790191
51. [51]
  Yu, T. R.; Ji, G. L.; Ding, C. P. Electrochemical Behavior of Variable Charge Soils, Vol. 2, Eds.:Yu, T. R.; Zhao, A. Z., Science Press, Beijing, 1996, p. 9(in Chinese).
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