工程科学学报，第40卷，第10期：1223-1230,2018年10月 Chinese Journal of Engineering,Vol.40,No.10:1223-1230,October 2018 DOI:10.13374/j.issn2095-9389.2018.10.009;http://journals.ustb.edu.cn 浸矿微生物氟抑制机理及铁的竞争络合作用 李想2)，温建康，莫晓兰)武彪，尚鹤，武名麟)，王淀佐)，杨洪英) 1)北京有色金属研究总院生物治金国家工程实验室，北京1000882)东北大学治金学院，沈阳110819 区通信作者，E-mail:kang3412@126.com 摘要含氟矿石中生物浸出技术推广应用存在瓶颈，究其原因在于伴随含氟脉石矿物溶解，氟对浸矿微生物有较强的抑制 作用.本研究利用氟的水化学特性，通过添加可形成稳定络合物的物质来转换F离子存在形态，进而使浸矿微生物可以耐受 高氟环境.本文系统研究了氟对细菌的抑制机理，明确了氟的真实毒性形态HF,发现了氟对细菌存在跨膜抑制作用，氟胁迫 条件下，干细胞内氟离子质量分数明显高于无氟对照组达到18%以上.选择在生物冶金体系中常见F·做为研究对象，研究 了F3·对F的络合解毒作用，热力学分析结果可知，F·可以与HF发生一级竞争络合反应，破坏HF络合结构.在铁离子存 在条件下，细菌最高可以耐受F·质量浓度1.0gL的环境下生长.铁氟络合形态分析可知，只有当培养基中F·质量浓度5 倍过量于F~质量浓度，细菌才能正常生长，对应的FF2·在氟化物中质量分数达45%时，而游离氟离子浓度为2.87×10~5 ol·L1.络合机理实验结果表明，根据配位化学原理，随着Fˉ/Fe3*浓度比的减小，配体浓度相对较低，氟与铁的络合物向低 配位方向移动，可以通过调整培养基中的氟铁浓度比来调整氟铁络合产物，使细菌在高氟环境中生长成为可能. 关键词氟抑制机理；铁；竞争络合；热力学；络合物形态控制 分类号TF88 Mechanism of fluoride inhibition on bioleaching bacteria and competitive complexation of ferric ions LI Xiang'),WEN Jian-kang),MO Xiao-lan'),WU Biao),SHANG He),WU Ming-lin,WANG Dian-zuo,YANG Hong- ying?) 1)National Engineering Laboratory of Biohydrometallurgy,General Research Institute for Nonferrous Metals,Beijing 100088,China 2)School of Metallurgy,Northeastern University,Shenyang 110819,China Corresponding author,E-mail:kang3412@126.com ABSTRACT A bottleneck occurs in the application of bioleaching technology to fluoride-containing ore.The reason for this is that fluorine has a strong inhibitory effect on leaching bacteria with the dissolution of fluorine-containing gangue minerals.In this study,we use the chemical properties of fluorine to convert F ions by adding substances that can form stable complexes with F-,which enables the leaching bacteria to tolerate high fluoride environments.In this research,we studied the inhibition mechanism of fluorine on bacte- ria,and identified its true toxic form(HF).We found that fluoride exhibited a transmembrane inhibitory effect on bacteria.Under flu- oride stress conditions,the concentration of intracellular fluoride was significantly higher than that of a non-fluorinated control group, which was about 18%dry cell.We selected common Feions in the bioleaching system,and studied the competitive complex detoxi- fication of Feto F-.Our thermodynamic analysis results show that Fecan compete with HF in first-order competitive complexation reactions whereby the HF complex structure is converted to FeF In the presence of ferric ions,we found that the bacteria could tol- erate F"concentrations up to 1.0gL.Our analysis of the Fe and F complex species indicates that bacteria could grow normally when the concentration of Feions was five times greater than that of Fions.Correspondingly,the proportion of Fecomponents in the 收稿日期：2018-05-18 基金项目：国家自然科学基金资助项目(51404031)工程科学学报,第 40 卷,第 10 期:1223鄄鄄1230,2018 年 10 月 Chinese Journal of Engineering, Vol. 40, No. 10: 1223鄄鄄1230, October 2018 DOI: 10. 13374 / j. issn2095鄄鄄9389. 2018. 10. 009; http: / / journals. ustb. edu. cn 浸矿微生物氟抑制机理及铁的竞争络合作用 李 想1,2) , 温建康1) 苣 , 莫晓兰1) , 武 彪1) , 尚 鹤1) , 武名麟1) , 王淀佐1) , 杨洪英2) 1) 北京有色金属研究总院生物冶金国家工程实验室, 北京 100088 2) 东北大学冶金学院, 沈阳 110819 苣通信作者, E鄄mail: kang3412@ 126. com 摘 要 含氟矿石中生物浸出技术推广应用存在瓶颈,究其原因在于伴随含氟脉石矿物溶解,氟对浸矿微生物有较强的抑制 作用. 本研究利用氟的水化学特性,通过添加可形成稳定络合物的物质来转换 F 离子存在形态,进而使浸矿微生物可以耐受 高氟环境. 本文系统研究了氟对细菌的抑制机理,明确了氟的真实毒性形态 HF,发现了氟对细菌存在跨膜抑制作用,氟胁迫 条件下,干细胞内氟离子质量分数明显高于无氟对照组达到 18% 以上. 选择在生物冶金体系中常见 Fe 3 + 做为研究对象,研究 了 Fe 3 + 对 F - 的络合解毒作用,热力学分析结果可知,Fe 3 + 可以与 HF 发生一级竞争络合反应,破坏 HF 络合结构. 在铁离子存 在条件下,细菌最高可以耐受 F - 质量浓度 1郾 0 g·L - 1的环境下生长. 铁氟络合形态分析可知,只有当培养基中 Fe 3 + 质量浓度 5 倍过量于 F - 质量浓度,细菌才能正常生长,对应的 FeF 2 + 在氟化物中质量分数达 45% 时,而游离氟离子浓度为 2郾 87 伊 10 - 5 mol·L - 1 . 络合机理实验结果表明,根据配位化学原理,随着 F - / Fe 3 + 浓度比的减小,配体浓度相对较低,氟与铁的络合物向低 配位方向移动,可以通过调整培养基中的氟铁浓度比来调整氟铁络合产物,使细菌在高氟环境中生长成为可能. 关键词 氟抑制机理; 铁; 竞争络合; 热力学; 络合物形态控制 分类号 TF88 收稿日期: 2018鄄鄄05鄄鄄18 基金项目: 国家自然科学基金资助项目(51404031) Mechanism of fluoride inhibition on bioleaching bacteria and competitive complexation of ferric ions LI Xiang 1,2) , WEN Jian鄄kang 1) 苣 , MO Xiao鄄lan 1) , WU Biao 1) , SHANG He 1) , WU Ming鄄lin 1) , WANG Dian鄄zuo 1) , YANG Hong鄄 ying 2) 1)National Engineering Laboratory of Biohydrometallurgy, General Research Institute for Nonferrous Metals, Beijing 100088, China 2)School of Metallurgy, Northeastern University, Shenyang 110819, China 苣Corresponding author, E鄄mail: kang3412@ 126. com ABSTRACT A bottleneck occurs in the application of bioleaching technology to fluoride鄄containing ore. The reason for this is that fluorine has a strong inhibitory effect on leaching bacteria with the dissolution of fluorine鄄containing gangue minerals. In this study, we use the chemical properties of fluorine to convert F ions by adding substances that can form stable complexes with F - , which enables the leaching bacteria to tolerate high fluoride environments. In this research, we studied the inhibition mechanism of fluorine on bacte鄄 ria, and identified its true toxic form (HF). We found that fluoride exhibited a transmembrane inhibitory effect on bacteria. Under flu鄄 oride stress conditions, the concentration of intracellular fluoride was significantly higher than that of a non鄄fluorinated control group, which was about 18% dry cell. We selected common Fe 3 + ions in the bioleaching system, and studied the competitive complex detoxi鄄 fication of Fe 3 + to F - . Our thermodynamic analysis results show that Fe 3 + can compete with HF in first鄄order competitive complexation reactions whereby the HF complex structure is converted to FeF 3 - n n . In the presence of ferric ions, we found that the bacteria could tol鄄 erate F - concentrations up to 1郾 0 g·L - 1 . Our analysis of the Fe and F complex species indicates that bacteria could grow normally when the concentration of Fe 3 + ions was five times greater than that of F - ions. Correspondingly, the proportion of FeF 2 + components in the