Rare Metals

, Volume 38, Issue 1, pp 87–94 | Cite as

Mechanism of aluminum complexation in oxidative activity of leaching bacteria in a fluoride-containing bioleaching system

  • Xiang Li
  • Jian-Kang WenEmail author
  • Xiao-Lan Mo
  • Wu Biao
  • Dian-Zuo Wang
  • Hong-Ying Yang


Accumulation of toxic ions in leachate is one factor limiting bioleaching applications. The effect of fluoride ions on the growth of bioleaching microorganisms has been extensively emphasized. In this study, HF is found to be the toxic form of fluoride that affects the bacterial activity under acidic conditions. The added aluminum could compete with H+ to complex with F, thus significantly decrease the concentration of HF and finally reduce the toxicity of fluoride to bacteria. When F/Al3+ concentration ratio is 0.5:1.0, Fe2+ oxidation rate could reach 0.167 g·L−1·h−1, close to that of the biotic control group (0.195 g·L−1·h−1). The competitive complexation mechanism of fluoride by \({\text{AlF}}_{n}^{3 - n}\) results in stability constants of \({\text{AlF}}_{n}^{3 - n}\) complex (7.00) that are larger than those of HF (3.18). The F/Al3+ concentration ratio in the medium could affect the speciation of \({\text{AlF}}_{n}^{3 - n}\) complex. With the decrease in F/Al3+ concentration ratio, the coordination numbers of \({\text{AlF}}_{n}^{3 - n}\) decrease. Finally, the feasibility of fluoride detoxification by aluminum ion is verified. This work has meaningful implications for fluoride-containing bacterial bioleaching systems.


Competitive complexation Detoxification Fluoride Aluminum Bioleaching 



This study was financially supported by the National Natural Science Foundation of China (Nos. 51404031 and U1608254).


  1. [1]
    Monnet A, Gabriel S, Percebois J. Long-term availability of global uranium resources. Resour Policy. 2017;53:394.CrossRefGoogle Scholar
  2. [2]
    Chen S, Xing W, Du X. Forecast of the demand and supply plan of China’s uranium resources till 2030. Int J Green Energy. 2017;14(7):638.CrossRefGoogle Scholar
  3. [3]
    Monnet A, Gabriel S, Percebois J. Analysis of the long-term availability of uranium: the influence of dynamic constraints and market competition. Energy Policy. 2017;105:98.CrossRefGoogle Scholar
  4. [4]
    Wen JK, Chen BW, Shang H, Zhang GC. Research progress in biohydrometallurgy of rare metals and heavy nonferrous metals with an emphasis on China. Rare Met. 2016;35(6):433.CrossRefGoogle Scholar
  5. [5]
    Mo XL, Wen JK, Chen BW, Wu ML, Zhang GC. Breeding of bacteria for high concentration fluoride-tolerance. Chin J Rare Metals. 2015;39(1):75.Google Scholar
  6. [6]
    Nadanaciva S, Weber J, Senior AE. Binding of the transition state analog MgADP-fluoroaluminate to F1-ATPase. J Biol Chem. 1999;274(11):7052.CrossRefGoogle Scholar
  7. [7]
    Bender GR, Thibodeau EA, Marquis RE. Reduction of acidurance of streptococcal growth and glycolysis by fluoride and gramicidin. J Dent Res. 1985;64(2):90.CrossRefGoogle Scholar
  8. [8]
    Brierley JA, Kuhn MC. Fluoride toxicity in a chalcocite bioleach heap process. Hydrometallurgy. 2010;104(3–4):410.CrossRefGoogle Scholar
  9. [9]
    Sicupira LC, Veloso TC, Reis F, Leão VA. Assessing metal recovery from low-grade copper ores containing fluoride. Hydrometallurgy. 2011;109(3–4):202.CrossRefGoogle Scholar
  10. [10]
    Mishra A, Pradhan N, Kar RN, Sukla LB, Mishraet BK. Microbial recovery of uranium using native fungal strains. Hydrometallurgy. 2009;95(1–2):175.CrossRefGoogle Scholar
  11. [11]
    Li Q, Ding DX, Sun J, Wang QL, Hu EM, Shi WG, Ma LY, Guo X, Liu XD. Community dynamics and function variation of a defined mixed bioleaching acidophilic bacterial consortium in the presence of fluoride. Ann Microbiol. 2015;65(1):121.CrossRefGoogle Scholar
  12. [12]
    Peng ZJ, Yu RL, Qiu GZ, Qin WQ, Gu GH, Wang QL, Li Q, Liu XD. Really active form of fluorine toxicity affecting Acidithiobacillus ferrooxidans activity in bioleaching uranium. Trans Nonferrous Metals Soc China. 2013;23(3):812.CrossRefGoogle Scholar
  13. [13]
    Wang YD, Ding DX, Li GY, Hu N. Continuous transfer domestication and associated domestication of Acidithiobacillus ferrooxidans for resistance of uranium and fluride ions. Chin J Process Eng. 2011;11(5):834.Google Scholar
  14. [14]
    Liu JH, Wu WR, Liu YJ, Sun ZX. Study on the fluorine resistance of Thiobacillus thiooxidans in uranium leaching. Metal Mine. 2009;395(5):50.Google Scholar
  15. [15]
    Mo XL, Li X, Wen JK, Cai LL. Bioleaching of uranium ore containing fluorite using Acidithiobacillus ferrivoran, Acidithiobacillus ferrooxidans and Leptospirillum ferriphilum. In: Proceedings of the 6th International Conference on Energy, Environment and Sustainable Development. Zhuhai; 2017. 1011.Google Scholar
  16. [16]
    Mo XL, Li X, Wen JK, Cai LL. Column bioleaching of fluorine-bearing uranium ore. In: Proceedings of the International Forum on Energy, Environment and Sustainable Development. Shenzhen; 2016. 992.Google Scholar
  17. [17]
    Liu SW, Chen JC, Chen GX, Sun ZX, Jiao XR. Matching test on bioleaching of fluorine-rich uranium ore. Nonferrous Metals (Extr Metall). 2014;(5):49.Google Scholar
  18. [18]
    Guo JY. Groundwater environmental evolution in Jilantai desert basin and safety risk control of drinking water in high fluoride area. Xi’an: Chang’an University; 2016. 65.Google Scholar
  19. [19]
    Pazand K. Geochemistry and multivariate statistical analysis for fluoride occurrence in groundwater in the Kuhbanan basin, Central Iran. Model Earth Syst Environ. 2016;2(2):1.CrossRefGoogle Scholar
  20. [20]
    Daniele L, Corbella M, Vallejos A, Díaz-Puga M, Pulido-Bosch A. Geochemical simulations to assess the fluorine origin in Sierra de Gador groundwater (SE Spain). Geofluids. 2013;13(2):194.CrossRefGoogle Scholar
  21. [21]
    Veloso TC, Sicupira LC, Rodrigues ICB, Silva LAM, Leão VA. The effects of fluoride and aluminum ions on ferrous-iron oxidation and copper sulfide bioleaching with Sulfobacillus thermosulfidooxidans. Biochem Eng J. 2012;62:48.CrossRefGoogle Scholar
  22. [22]
    Wu J, Li P, Qian H. Hydrochemical characterization of drinking groundwater with special reference to fluoride in an arid area of China and the control of aquifer leakage on its concentrations. Environ Earth Sci. 2015;73(12):8575.CrossRefGoogle Scholar
  23. [23]
    Ning ZQ, Zhai YC, Xie HW, Song QS, Yu K. Recovery of silica from sodium silicate solution of calcined boron mud. Rare Met. 2016;35(2):204.CrossRefGoogle Scholar
  24. [24]
    Ma LY, Wang XJ, Tao JM, Feng X, Liu XD, Qin WQ. Differential fluoride tolerance between sulfur- and ferrous iron-grown Acidithiobacillus ferrooxidans and its mechanism analysis. Biochem Eng J. 2017;119:59.CrossRefGoogle Scholar
  25. [25]
    Ma LY, Li Q, Shen L, Feng X, Xiao YH, Tao JM, Liang YL, Yin HQ, Liu XD. Insights into the fluoride-resistant regulation mechanism of Acidithiobacillus ferrooxidans ATCC 23270 based on whole genome microarrays. J Ind Microbiol Biotechnol. 2016;43(10):1441.CrossRefGoogle Scholar
  26. [26]
    Dean JA. Lange’s Handbook of Chemistry. New York: McGraw-Hill Professional Publishing; 1999. 924.Google Scholar
  27. [27]
    Gutknecht J, Walter A. Hydrofluoric and nitric acid transport through lipid bilayer membranes. Biochim Biophys Acta Biomembr. 1981;644(1):153.CrossRefGoogle Scholar
  28. [28]
    Nadanaciva S, Weber J, Senior AE. Binding of the transition state analog MgADP-fluoroaluminate to F1-ATPase. J Biol Chem. 1999;274(11):7052.CrossRefGoogle Scholar
  29. [29]
    Cate JMT, Van LC. Fluoride mechanisms. Dent Clin North Am. 1999;43(4):713.Google Scholar
  30. [30]
    Suzuki I, Lee D, Mackay B, Harahuc L, Oh JK. Effect of various ions, pH and osmotic pressure on oxidation of elemental sulfur by Thiobacillus thiooxidans. Appl Environ Microbiol. 1999;65(11):5163.Google Scholar
  31. [31]
    Dopson M, Lövgrenb L, Boström D. Silicate mineral dissolution in the presence of acidophilic microorganisms: implications for heap bioleaching. Hydrometallurgy. 2009;96(4):288.CrossRefGoogle Scholar
  32. [32]
    Deng YM, Nordstrom DK, McCleskey RB. Fluoride geochemistry of thermal waters in Yellowstone National Park: I. Aqueous fluoride speciation. Geochim Cosmochim Acta. 2011;75(16):4476.CrossRefGoogle Scholar

Copyright information

© The Nonferrous Metals Society of China and Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.National Engineering Laboratory of BiohydrometallurgyGeneral Research Institute for Nonferrous MetalsBeijingChina
  2. 2.School of MetallurgyNortheastern UniversityShenyangChina

Personalised recommendations