Cl~-/SO_4~(2-)铁盐对含可溶性胞外多聚物Acidithiobacillus ferrooxidans溶液中铁矿物形成的影响
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摘要
铁细菌胞外多聚物作用下聚集的铁可通过氧化或者沉淀作用使铁稳定或沉积,从而形成铁矿物。本文基于铁细菌胞外多聚物(extracellular polymeric substances,EPS)对铁矿物形成的调控作用,介绍了Cl-/SO_4~(2-)的Fe(Ⅲ)或Fe(Ⅱ)盐作用下,含可溶性EPS的氧化亚铁硫杆菌(Acidithiobacillus ferrooxidans)溶液中铁矿物的形成,观察了溶液pH值变化及形成铁矿物的矿相与结构,并采用XRD、FTIR和FESEM对其进行表征。结果发现反应溶液中OH-离子可与Fe3+形成微米级"针垫"聚集球状或纳米级小球形施威特曼石和微米级"菱形"块状黄钾铁矾铁矿物沉淀。反应溶液中的可溶性EPS可调控和促进铁矿物的形成,但对Fe2+的氧化未产生影响;外源Fe盐可促进施威特曼石向黄钾铁矾转化。随着Cl-/SO_4~(2-)摩尔比例的增加(即Cl-含量的不断增加),两矿相间的转化明显受到抑制,且铁矿物颗粒之间的集聚作用明显减弱;反之,SO_4~(2-)含量升高时,有利于铁矿物间的转化和聚集球状颗粒形貌结构的形成。
Extracellular polymeric substances(EPS) extracted from iron bacteria can promote the iron aggregation and then form iron minerals by stabilization and deposition actions of ferric ions. In this paper, based on the key regulation or influence on ferric bio-mineralization by iron bacteria or their EPS, the authors introduced the biomineralization formation of iron oxyhydroxides in soluble EPS-containing solutions from Acidithiobacillus ferrooxidans cultures without/with Fe(Ⅱ) or Fe(Ⅲ) at various molar rates of Cl-/SO_4~(2-). It mainly described the change of solution pH values and the phases and structures of the formed iron minerals characterized by XRD, FTIR and FESEM. The decrease of solution pH values and the characterization results suggested that the micro-sphere schwertmannite covered by "pincushion" or nano-spheroid schwertmannite and micro-prism jarosite particles could form in all reaction solutions. The resulting iron precipitates uld be regulated by bacterial EPS, which, however, hardly had impact on ferrous oxidation, and addition of iron salts could promote the transformation of initial schwertmannite into jarosite phase. It was also demonstrated that phase transformation and particle agglomeration could be prevented with the increase of Cl-/SO_4~(2-) molar ratios(i. e. increase of Cl-content). This might be related to the higher SO_4~(2-) content occurring in the reaction solutions, which facilitated phase transformation of iron minerals and presence of the tightly assembled spheroid particle morphology.
Extracellular polymeric substances(EPS) extracted from iron bacteria can promote the iron aggregation and then form iron minerals by stabilization and deposition actions of ferric ions. In this paper, based on the key regulation or influence on ferric bio-mineralization by iron bacteria or their EPS, the authors introduced the biomineralization formation of iron oxyhydroxides in soluble EPS-containing solutions from Acidithiobacillus ferrooxidans cultures without/with Fe(Ⅱ) or Fe(Ⅲ) at various molar rates of Cl-/SO_4~(2-). It mainly described the change of solution pH values and the phases and structures of the formed iron minerals characterized by XRD, FTIR and FESEM. The decrease of solution pH values and the characterization results suggested that the micro-sphere schwertmannite covered by "pincushion" or nano-spheroid schwertmannite and micro-prism jarosite particles could form in all reaction solutions. The resulting iron precipitates uld be regulated by bacterial EPS, which, however, hardly had impact on ferrous oxidation, and addition of iron salts could promote the transformation of initial schwertmannite into jarosite phase. It was also demonstrated that phase transformation and particle agglomeration could be prevented with the increase of Cl-/SO_4~(2-) molar ratios(i. e. increase of Cl-content). This might be related to the higher SO_4~(2-) content occurring in the reaction solutions, which facilitated phase transformation of iron minerals and presence of the tightly assembled spheroid particle morphology.
引文
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Sivkov A,Naiden E,Ivashutenko A,et al.2015.Plasma dynamic synthesis and obtaining ultrafine powders of iron oxides with high content ofε-Fe2O3[J].Journal of Magnetism and Magnetic Materials,405:158~168.
Tan Jianxi.2009.Effects of extracellular polymers on leaching of chalcopyrite from Acidicthiobacillus ferrooxidans[D].Hunan:Central South University(in Chinese with English abstract).
Wang M and Zhou L X.2012.Simultaneous oxidation and precipitation of iron using jarosite immobilized Acidithiobacillus ferrooxidans,and its relevance to acid mine drainage[J].Hydrometallurgy,125~126(8):152~156.
Xiong Huixin and Guo Ron.2011.Effects of chloride acclimation on iron oxyhydroxides and cell morphology during cultivation of Acidithiobacillus ferrooxidans[J].Environmental Science and Technology,45:235~240.
Xu Yiqun,Gu Yuanyuan,Yao Ting,et al.2013.Regulating formation of iron minerals by iron bacteria/EPS and its environmental significance[J].Acta Petrologica et Mineralogica,32(6):782~788(in Chinese with English abstract).
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Yu R L,Zhong D L,Miao L,et al.2011.Relationship and effect of redox potential,jarosites and extracellular polymeric substances in bioleaching chalcopyrite by Acidithiobacillus ferrooxidans[J].Transaction of Nonferrous Metals Society of China,21(7):1 634~1 640.
Yu Yanyun.2014.Effects of extracellular polymers on the interface of iron minerals with microorganisms[D].Hefei:Hefei University of Technology(in Chinese with English abstract).
Yu Zhibo,Liu Yajie,Wu Jianglin,et al.2016.Review on extracellular polymer substances of bacteria on bioleaching[J].Nonferrous Metals(Extractive Metallurgy),2:1~6(in Chinese with English abstract).
Zheng Huaili,Xie Liguo,Gao Chaoyong,et al.2009.Study on the hydrolysis distribution of ferric saline by infrared spectrophotometry and single crystal X-ray diffraction method[J].Spectroscopy and Spectral Analysis,29(2):540~543(in Chinese with English abstract).
Zhu J Y,Gan M,Zhang D,et al.2013.The nature of schwertmannite and jarosite mediated by two strains of Acidithiobacillus ferrooxidans with different ferrous oxidation ability[J].Materials Science and Engineering C,33(5):2 679~2 685.
梁剑茹,柏双友,崔春红.2011.不同初始Fe(Ⅱ)浓度对施威特曼石生物合成的影响[J].岩石矿物学杂志,30(6):1 046~1 052.
鲁安怀.2007.生命活动中矿化作用的环境响应机制研究[J].高校地质学报,13(4):613~620.
鲁安怀,王长秋,李艳.2012.生命活动过程中无机矿化作用现象及其环境效应[J].科学,64(4):14~17.
谭建锡.2009.胞外多聚物对嗜酸氧化亚铁硫杆菌浸出黄铜矿的影响初探[D].湖南:中南大学.
徐轶群,顾园园,姚婷,等.2013.铁细菌胞外多聚物对铁矿物的调控形成及其环境意义[J].岩石矿物学杂志,32(6):782~788.
虞艳云.2014.胞外聚合物在含铁矿物同微生物界面过程中的作用研究[D].合肥:合肥工业大学.
余志波,刘亚洁,吴静琳,等.2016.生物浸矿过程中细菌胞外聚合物的作用研究进展[J].有色金属(冶炼部分),2:1~6.
郑怀礼,谢礼国,高朝勇,等.2009.红外光谱法及单晶X衍射法研究Fe(Ⅲ)水解形态分布[J].光谱学与光谱分析,29(2):540~543.
Cao Y Y,Wei X,Cai P,et al.2011.Preferential adsorption of extracellular polymeric substances from bacteria on clay minerals and iron oxide[J].Colloids and Surfaces B:Biointerfaces,83(1):122~127.
Chan C S,Fakra S C,Emerson D,et al.2011.Lithotrophic iron-oxidizing bacteria produce organic stalks to control mineral growth:implications for biosignature formation[J].The Isme Journal,5(4):717~727.
Huang S and Zhou L X.2012.Fe2+oxidation rate drastically affect the formation and phase of secondary iron hydroxysulfate mineral occurred in acid mine drainage[J].Materials Science and Engineering C,32(4):916~921.
Jin J and Guan Y.2014.The mutual co-regulation of extracellular polymeric substances and iron ions in biocorrosion of cast iron pipes[J].Bioresource Technology,169(5):387~394.
Liang Jianru,Bai Shuangyou and Cui Chunhong.2011.The effects of initial Fe(Ⅱ)concentrations on the biosynthesis of schwertmannite[J].Acta Petrologica et Mineralogica,30(6):1 046~1 052(in Chinese with English abstract).
Liao Y H,Zhou L X,Bai S Y,et al.2009.Occurrence of biogenic schwertmannite in sludge bioleaching environments and its adverse effect on solubilization of sludge-borne metals[J].Applied Geochemistry,24(9):1 739~1 746.
Liu F W,Zhou J,Zhou L X,et al.2015.Effect of neutralized solid waste generated in lime neutralization on the ferrous ion bio-oxidation process during acid mine drainage treatment[J].Journal of Hazardous Materials,299:404~411.
Liu H,Li P,Lu B,et al.2009.Transformation of ferrihydrite in the presence or absence of trace Fe(Ⅱ):the effect of preparation procedures of ferrihydrite[J].Journal of Solid State Chemistry,182(7):1 767~1 771.
Lu Anhuai.2007.Mechanisms of environmental response to biomineralization[J].Geological Journal of China Universities,13(4):613~620(in Chinese with English abstract).
Lu Anhuai,Wang Changqiu and Li Yan.2012.Inorganic mineralization and its environmental effects during life activities[J].Science,64(4):14~17(in Chinese).
Miao H,Li J,Lin Y Q,et al.2011.Characterization ofγ-Fe2O3nanoparticles prepared by transformation ofα-Fe OOH[J].Chinese Science Bulletin,56(22):2 383~2 388.
Singh M,Rajesh V J,Sajinkumar K S,et al.2016.Spectral and chemical characterization of jarosite in a palaeolacustrine depositional environment in warkalli formation in Kerala,South India and its implications[J].Spectrochimica Acta Part A Molecular and Biomolecular Spectroscopy,168:86~97.
Sivkov A,Naiden E,Ivashutenko A,et al.2015.Plasma dynamic synthesis and obtaining ultrafine powders of iron oxides with high content ofε-Fe2O3[J].Journal of Magnetism and Magnetic Materials,405:158~168.
Tan Jianxi.2009.Effects of extracellular polymers on leaching of chalcopyrite from Acidicthiobacillus ferrooxidans[D].Hunan:Central South University(in Chinese with English abstract).
Wang M and Zhou L X.2012.Simultaneous oxidation and precipitation of iron using jarosite immobilized Acidithiobacillus ferrooxidans,and its relevance to acid mine drainage[J].Hydrometallurgy,125~126(8):152~156.
Xiong Huixin and Guo Ron.2011.Effects of chloride acclimation on iron oxyhydroxides and cell morphology during cultivation of Acidithiobacillus ferrooxidans[J].Environmental Science and Technology,45:235~240.
Xu Yiqun,Gu Yuanyuan,Yao Ting,et al.2013.Regulating formation of iron minerals by iron bacteria/EPS and its environmental significance[J].Acta Petrologica et Mineralogica,32(6):782~788(in Chinese with English abstract).
Xu Z Z,Liang J R and Zhou L X.2013.Photo-Fenton-like degradation of azo dye methyl orange using synthetic ammonium and hydronium jarosite[J].Journal of Alloys and Compounds,546(1):112~118.
Yan W,Liu H,Chen R,et al.2015.Dissolution and oriented aggregation:transformation from lepidorocite to goethite by the catalysis of aqueous Fe(Ⅱ)[J].RSC Advances,5(129):106 396~106 399.
Yang L,Steefel C I,Marcus M A,et al.2010.Kinetics of Fe(Ⅱ)-catalyzed transformation of 6-line ferrihydrite under anaerobic flow conditions[J].Environmental Science and Technology,44(14):5 469~5 475.
Yu R L,Zhong D L,Miao L,et al.2011.Relationship and effect of redox potential,jarosites and extracellular polymeric substances in bioleaching chalcopyrite by Acidithiobacillus ferrooxidans[J].Transaction of Nonferrous Metals Society of China,21(7):1 634~1 640.
Yu Yanyun.2014.Effects of extracellular polymers on the interface of iron minerals with microorganisms[D].Hefei:Hefei University of Technology(in Chinese with English abstract).
Yu Zhibo,Liu Yajie,Wu Jianglin,et al.2016.Review on extracellular polymer substances of bacteria on bioleaching[J].Nonferrous Metals(Extractive Metallurgy),2:1~6(in Chinese with English abstract).
Zheng Huaili,Xie Liguo,Gao Chaoyong,et al.2009.Study on the hydrolysis distribution of ferric saline by infrared spectrophotometry and single crystal X-ray diffraction method[J].Spectroscopy and Spectral Analysis,29(2):540~543(in Chinese with English abstract).
Zhu J Y,Gan M,Zhang D,et al.2013.The nature of schwertmannite and jarosite mediated by two strains of Acidithiobacillus ferrooxidans with different ferrous oxidation ability[J].Materials Science and Engineering C,33(5):2 679~2 685.
梁剑茹,柏双友,崔春红.2011.不同初始Fe(Ⅱ)浓度对施威特曼石生物合成的影响[J].岩石矿物学杂志,30(6):1 046~1 052.
鲁安怀.2007.生命活动中矿化作用的环境响应机制研究[J].高校地质学报,13(4):613~620.
鲁安怀,王长秋,李艳.2012.生命活动过程中无机矿化作用现象及其环境效应[J].科学,64(4):14~17.
谭建锡.2009.胞外多聚物对嗜酸氧化亚铁硫杆菌浸出黄铜矿的影响初探[D].湖南:中南大学.
徐轶群,顾园园,姚婷,等.2013.铁细菌胞外多聚物对铁矿物的调控形成及其环境意义[J].岩石矿物学杂志,32(6):782~788.
虞艳云.2014.胞外聚合物在含铁矿物同微生物界面过程中的作用研究[D].合肥:合肥工业大学.
余志波,刘亚洁,吴静琳,等.2016.生物浸矿过程中细菌胞外聚合物的作用研究进展[J].有色金属(冶炼部分),2:1~6.
郑怀礼,谢礼国,高朝勇,等.2009.红外光谱法及单晶X衍射法研究Fe(Ⅲ)水解形态分布[J].光谱学与光谱分析,29(2):540~543.