不同条件下形成的黄钾铁矾微形貌对比研究
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摘要
黄钾铁矾是酸性矿山废水(AMD)中常见的次生矿物,能有效吸附AMD中Cu、Pb、Zn、Gd、As等重金属元素。不同条件下形成的黄钾铁矾微形貌不同,其吸附能力也不同。文章通过化学法和微生物法合成了黄钾铁矾,并在粤北大宝山矿酸性矿山废水中采集了含黄钾铁矾的泥样。利用扫描电镜-能谱分析(SEM)和X光衍射(XRD),对三种不同条件下形成的黄钾铁矾进行鉴定和微形貌特征观察,并分析黄钾铁矾的形成条件。结果表明,常温条件下,pH值2.0～2.5时能够化学合成黄钾铁矾,其晶体粒径约2～10μm,且晶形呈板状;而在65℃时,可在pH2.0～3.0之间化学合成黄钾铁矾,但晶形差。微生物法合成黄钾铁矾pH范围是2.0～5.0,其晶形完好,呈菱面体且晶体大小比较均匀,而约为2～4μm。酸性矿山废水中的黄钾铁矾形成的pH值为2.5～3.5,晶形为菱面体形,单个晶体大小多为1～2μm。根据其形成条件和微形貌特征,文章推测酸性矿山废水中形成的黄钾铁矾可能是微生物成因。
Jarosite is a very common secondary mineral in acid mine drainage(AMD). It can absorb effectively heavy metallic elements such as Pb, Zn, Gd, As in AMD. The jarosite formed under different conditions is of diverse microtopography and different adsorption capacities to heavy metallic ions. In this paper, jarosite was synthesized by chemical and microbiological methods, respectively, and the samples of sediments with jarosite-bearing secondary minerals were collected form the AMD of Dabaoshan Mine in the north Guangdong Province. The jarosite formed under different conditions was identified by using SEM and XRD, its microtopographic characteristics were observed, and the synthesis conditions of jarosite were investigated. The results show that the range of pH values in which jarosite can be chemically synthesized is approximately 2.0-2.5 at room temperatures. The crystal size of the synthetic jarosite is about 2-10 μm and the crystalline form is plate-like. Jarosite can also be chemically synthesized at 65℃ with a wider range of pH values between 2.0-3.0, but the crystalline form is relatively poor. Jarosite can be synthesized by microbial method in a relatively large range of pH values between 2.0-5.0, which has nearly perfect rhombohedron-shape crystalline form and relatively uniform sizes about2-4 μm. Jarosite discovered in sediments of AMD occurs in a pH value ranging from 2.5 to 3.5. It is of relatively perfect rhombohedron-shape crystal and the single crystal size is mostly in1-2 μm. According to the formation conditions and microtopographic characteristics, the jarosite formed in AMD is probably of microbial origin.
Jarosite is a very common secondary mineral in acid mine drainage(AMD). It can absorb effectively heavy metallic elements such as Pb, Zn, Gd, As in AMD. The jarosite formed under different conditions is of diverse microtopography and different adsorption capacities to heavy metallic ions. In this paper, jarosite was synthesized by chemical and microbiological methods, respectively, and the samples of sediments with jarosite-bearing secondary minerals were collected form the AMD of Dabaoshan Mine in the north Guangdong Province. The jarosite formed under different conditions was identified by using SEM and XRD, its microtopographic characteristics were observed, and the synthesis conditions of jarosite were investigated. The results show that the range of pH values in which jarosite can be chemically synthesized is approximately 2.0-2.5 at room temperatures. The crystal size of the synthetic jarosite is about 2-10 μm and the crystalline form is plate-like. Jarosite can also be chemically synthesized at 65℃ with a wider range of pH values between 2.0-3.0, but the crystalline form is relatively poor. Jarosite can be synthesized by microbial method in a relatively large range of pH values between 2.0-5.0, which has nearly perfect rhombohedron-shape crystalline form and relatively uniform sizes about2-4 μm. Jarosite discovered in sediments of AMD occurs in a pH value ranging from 2.5 to 3.5. It is of relatively perfect rhombohedron-shape crystal and the single crystal size is mostly in1-2 μm. According to the formation conditions and microtopographic characteristics, the jarosite formed in AMD is probably of microbial origin.
引文
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黄珊.2011.黄钾铁矾生物合成的影响因素及其机制研究[D].南京:南京农业大学:50-56.
李中春.2014.制备黄钾铁矾的方法[P].中国:CN 103922417A.
陆建军,陆现彩,朱长见,等.2005.氧化亚铁硫杆菌对矿山酸矿水中金属污染元素分布的影响[J].南京大学学报:自然科学,41(2):113-119.
万淑娟,党志.2010.一株氧化亚铁硫杆菌的筛选及生长条件研究[J].环境工程学报,49(5):146-149.
王长秋,马生凤,鲁安怀,等.2006.黄钾铁矾类矿物沉淀去除Cr(VI)的初步研究[J].矿物岩石地球化学通报,25(4):335-338.
王智美,陈炳辉,江春苗,等.2010.粤北大宝山酸性矿山废水氧化亚铁硫杆菌及其相关性能研究[J].中山大学学报(自然科学版),9(4):2176-2150.
刘奇缘,陈炳辉,周永章,等.2017.粤北大宝山槽对坑酸性矿山废水中不同沉积层次生矿物研究[J].地球与环境,45(3):259-266.
Banfield J F,Welch S A,Zhang H Z,et al.2000.Crystal growth and microstructure development in natural iron oxyhy droxide biomineralization products[J].Science,289:75 1-754.
Bauer A and Velde B.1997.Jarosite formation in weathered siliceous chalk in Fontevrault abbey,Loire Valley,France[J].Mineralogical Magazine,61:705-711.
Bigham J M, Schwertmann U, Pfab G,et al.1996.Influence of pH on mineral speciation in a bioreac.tor simulating acid mine drainage[J].Applied Geochemistry,11:845-849.
Carbone C,Dinelli E,Marescotti P,et al.2013.The role of AMD secondary minerals in controlling environmental pollution:Indications from bulk leaching tests[J].Journal of Geochemical Exploration,132:188-200.
Carlson L,Lindstrom E B,Hallberg K B,et al.1992.Solid-phase products of bacterial oxidation of arsenical pyrite[J].Applied and Environmental Microbiology,58:1046-1049.
Das A and Modak J M.1997.Studies on multi-metal ion tolerance of Thiobacillus ferrooxidans[J].Mineral Engineering,10(7):743-749.
Dutrizac J E and Kaiman S.1976.Synthesis and properties of jarosite-type compounds[J].Can Mineral,14(2):151-158.
Espana J S,Pamo E L,Santofimia E,et al.2005.Acid mine drainage in the Iberian Pyrite Belt(Odiel river watershed,Huelva,SW Spain):geochemistry,mineralogy and environmental implications[J].Applied Geochemistry,20:1320-1356.
Gagliano W B,Brill M R,Bigham J M,et al.2004.Chemistry and mineralogy of ochreous sediments in a constructed mine drainage wetland[J].Geochim Cosmochim Acta,68(9):2119-2128.
Grishin S I and Bigham J M.1988.Characterization of jarosite formed uponbacterial oxidation of ferrous sulfate in a packed-bed reactor[J].Applied and Environmental Miorobiology,54(12):3101-3106.
Marescotti P, Carbone C,Comodi P,et al.2012.Mineralogical and chemical evolution of ochreous precipitates from the Libiola Fe-Cu-sulfide mine(Eastern Liguria,Italy)[J].Geochemistry,10(27):577-589.
Niemel S I,Riekkola-Vanhanen M,Sivel C,et al.1994.Nutrient effect on the biological leaching of a black-schist ore[J].Applied environment Microbiology,60(4):1287-129 1.
Nieva N E,Borgnino L,Locati F,et al.2016.Mineralogical control on arsenic release during sediment-water interaction in abandoned mine wastes from the Argentina Puna[J].Science of the Total Environment,550:1141-1151.
Sasaki K and Konno H.2000.Morphology of jarosite-group compounds precipitated from biologically and chemically oxidized Fe ion[J].The Canadian Mineralogist,38:45-66.
Valente T,Grande J A,Ceron J C,et al.2013.Mineralogy and environmental relevance of AMD-precipitates from the Tharsis mines,Iberian Pyrite Belt(SW,Spain)[J].Applied Geochemistry,39:11-25.
Wang Honlgmei,Bigham J M and Tuovinen O H.2006.Formation of schwertmannite and its transformation to jarosite in the presence of acidophilic iron-oxidizing microorganisms[J].Materials Science and Engineering,26:588-592.
段星春,王义锦,党志,等.2007.大宝山矿区水体中重金属的行为研究[J].地球与环境,35(3):255-260.
黄珊.2011.黄钾铁矾生物合成的影响因素及其机制研究[D].南京:南京农业大学:50-56.
李中春.2014.制备黄钾铁矾的方法[P].中国:CN 103922417A.
陆建军,陆现彩,朱长见,等.2005.氧化亚铁硫杆菌对矿山酸矿水中金属污染元素分布的影响[J].南京大学学报:自然科学,41(2):113-119.
万淑娟,党志.2010.一株氧化亚铁硫杆菌的筛选及生长条件研究[J].环境工程学报,49(5):146-149.
王长秋,马生凤,鲁安怀,等.2006.黄钾铁矾类矿物沉淀去除Cr(VI)的初步研究[J].矿物岩石地球化学通报,25(4):335-338.
王智美,陈炳辉,江春苗,等.2010.粤北大宝山酸性矿山废水氧化亚铁硫杆菌及其相关性能研究[J].中山大学学报(自然科学版),9(4):2176-2150.
刘奇缘,陈炳辉,周永章,等.2017.粤北大宝山槽对坑酸性矿山废水中不同沉积层次生矿物研究[J].地球与环境,45(3):259-266.
Banfield J F,Welch S A,Zhang H Z,et al.2000.Crystal growth and microstructure development in natural iron oxyhy droxide biomineralization products[J].Science,289:75 1-754.
Bauer A and Velde B.1997.Jarosite formation in weathered siliceous chalk in Fontevrault abbey,Loire Valley,France[J].Mineralogical Magazine,61:705-711.
Bigham J M, Schwertmann U, Pfab G,et al.1996.Influence of pH on mineral speciation in a bioreac.tor simulating acid mine drainage[J].Applied Geochemistry,11:845-849.
Carbone C,Dinelli E,Marescotti P,et al.2013.The role of AMD secondary minerals in controlling environmental pollution:Indications from bulk leaching tests[J].Journal of Geochemical Exploration,132:188-200.
Carlson L,Lindstrom E B,Hallberg K B,et al.1992.Solid-phase products of bacterial oxidation of arsenical pyrite[J].Applied and Environmental Microbiology,58:1046-1049.
Das A and Modak J M.1997.Studies on multi-metal ion tolerance of Thiobacillus ferrooxidans[J].Mineral Engineering,10(7):743-749.
Dutrizac J E and Kaiman S.1976.Synthesis and properties of jarosite-type compounds[J].Can Mineral,14(2):151-158.
Espana J S,Pamo E L,Santofimia E,et al.2005.Acid mine drainage in the Iberian Pyrite Belt(Odiel river watershed,Huelva,SW Spain):geochemistry,mineralogy and environmental implications[J].Applied Geochemistry,20:1320-1356.
Gagliano W B,Brill M R,Bigham J M,et al.2004.Chemistry and mineralogy of ochreous sediments in a constructed mine drainage wetland[J].Geochim Cosmochim Acta,68(9):2119-2128.
Grishin S I and Bigham J M.1988.Characterization of jarosite formed uponbacterial oxidation of ferrous sulfate in a packed-bed reactor[J].Applied and Environmental Miorobiology,54(12):3101-3106.
Marescotti P, Carbone C,Comodi P,et al.2012.Mineralogical and chemical evolution of ochreous precipitates from the Libiola Fe-Cu-sulfide mine(Eastern Liguria,Italy)[J].Geochemistry,10(27):577-589.
Niemel S I,Riekkola-Vanhanen M,Sivel C,et al.1994.Nutrient effect on the biological leaching of a black-schist ore[J].Applied environment Microbiology,60(4):1287-129 1.
Nieva N E,Borgnino L,Locati F,et al.2016.Mineralogical control on arsenic release during sediment-water interaction in abandoned mine wastes from the Argentina Puna[J].Science of the Total Environment,550:1141-1151.
Sasaki K and Konno H.2000.Morphology of jarosite-group compounds precipitated from biologically and chemically oxidized Fe ion[J].The Canadian Mineralogist,38:45-66.
Valente T,Grande J A,Ceron J C,et al.2013.Mineralogy and environmental relevance of AMD-precipitates from the Tharsis mines,Iberian Pyrite Belt(SW,Spain)[J].Applied Geochemistry,39:11-25.
Wang Honlgmei,Bigham J M and Tuovinen O H.2006.Formation of schwertmannite and its transformation to jarosite in the presence of acidophilic iron-oxidizing microorganisms[J].Materials Science and Engineering,26:588-592.
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