Mineralogical Characteristics of Ankerite and Mechanisms of Primary and Secondary Origins
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摘要: 长期以来，铁白云石的命名划分标准混乱，一直被当成高温及次生的产物.综述了国内外铁白云石的研究进展，详细探讨了铁白云石的矿物学特征，特别在其成因中加入了微生物因素，运用地质微生物学探讨原生铁白云石的成因机制.研究认为：（1）铁白云石命名划分依据应遵照国际矿物学会的原则，以铁是否替代白云石晶格中半数镁的位置为标准，分为白云石和铁白云石；（2）详述铁白云石矿物学及其晶体特征；（3）铁白云石成因分为原生沉淀及次生两种，微生物介导形成原生白云石的过程中，有助于铁进入到白云石晶格中，增加晶格中铁的含量.Abstract: The compositional break between ferroan dolomite and ankerite has not been well-defined for a long time. Ankerite has always been regarded as a secondary mineral generated at high temperatures. In this paper, progress in mineralogy and origins of ankerite and a link between microbial activity and ankerite are evaluated. Based on documented data:(1) The compositional break based on the "50% rule" principle from International Association of Mineralogy is applied for Ca-Mg-Fe carbonate. Any minerals with more than 50 mol% Fe in the Mg site would be called ankerite; (2) Progresses in mineralogical and lattice characteristics of ankerite are presented; (3) The origins of ankerite are primary and secondary. In the process of microbial mediated primary dolomite, microbe facilitates iron into the dolomite lattice and increases the iron content in the Mg site in its structure. Microbes could be added into the primary sedimentary experiments to promote mediation of the primary ankerite.
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Key words:
- ankerite /
- primary ankerite /
- microbial origin /
- mineralogy
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图 1 理想的有序白云石晶体结构图及铁离子的位置
Fig. 1. Atomic structure of an idealized stoichiometric dolomite crystal and preferred sites for elemental substitution of Fe
图 2 次生的铁白云石
a.奥陶系马五段陕338井中，膏溶铸模孔中被后期次生形成的铁白云石充填(张军涛等，2017)；b~d.波兰西里西亚盆地始新世-渐新世自生白云岩地层，多种多样不同期次的铁白云石胶结物(Bojanowski, 2014)
Fig. 2. Secondary ankerite
图 3 微生物到铁矿物的电子传递机制
Fig. 3. Mechanisms of electron transfer from microorganisms to Fe (Ⅲ) minerals
图 4 微生物培养实验中含铁量高的白云石SEM图像
Fig. 4. SEM secondary electron images of ferroan dolomite in the bacterial cultural experiments
表 1 双舱法合成铁白云岩固溶体的混合物和晶胞参数
Table 1. Composition and unit-cell parameters of the ankerite solid solutions in double-capsule method synthesized experiments
样品 x a(Å) c(Å) V(Å3) CaMg(CO3)2 0 4.807 6(3) 16.007 0(2) 320.40 ank1 0.158 3 4.810 2(6) 16.052 4(43) 321.66 ank2 0.299 0 4.810 8(2) 16.109 5(17) 322.88 ank3 0.499 6 4.813 1(1) 16.120 0(9) 323.41 ank4 0.648 0 4.818 2(8) 16.154 3(5) 324.79 ank5 1.000 0 4.830 0(9) 16.221 0(8) 327.72 CaFe(CO3)2 1.000 0 4.829 1(3) 16.210 0(1) 327.38 注：表中数据源于Chai and Navrotsky(1996)；x.Ca(FexMg1- x)(CO3)2；a和c.晶胞参数；V.晶胞体积. 
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表 2 不同压力下白云石与铁白云石的晶胞参数
Table 2. Unit-cell parameters of dolomite and ankerite under different pressures
压力(GPa) 白云石晶胞参数 a(Å) c(Å) V(Å3) 0.00 4.806 4(5) 16.006(2) 320.22(8) 0.47 4.802 8(7) 16.962(2) 318.87(9) 1.50 4.791 0(7) 15.856(2) 315.20(9) 2.34 4.784 3(9) 15.785(2) 312.90(11) 2.90 4.777 7(5) 15.730(1) 310.97(6) 3.70 4.770 3(7) 15.653(2) 308.47(10) 4.20 4.767 2(6) 15.611(2) 307.24(8) 4.69 4.763 6(5) 15.582(3) 306.21(8) 压力(GPa) 铁白云石晶胞参数 a(Å) c(Å) V(Å3) 0.00 4.836 0(8) 16.186(2) 327.82(11) 0.97 4.826 5(8) 16.085(2) 324.51(11) 1.90 4.816 3(6) 15.992(2) 321.26(9) 2.56 4.810 9(6) 15.924(2) 319.18(8) 2.97 4.807 0(6) 15.881(2) 317.81(8) 3.40 4.803 8(8) 15.847(2) 316.71(10) 4.00 4.799 0(6) 15.792(2) 314.97(8) 注：表中数据源于Ross and Reeder(1992)；a和c.晶胞参数；V.晶胞体积.
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表 3 标准白云石、铁白云石衍射数据(ICDD数据)
Table 3. Standard XRD data of dolomite and ankerite from ICDD
标准白云石 标准铁白云石 d I/I0 hkl d I/I0 hkl 4.033 1 101 4.051 ＜1 101 3.699 3 012 3.714 2 012 2.888 100 104 2.906 100 104 2.670 4 006 2.693 4 006 2.539 3 015 2.556 ＜1 015 2.404 8 110 2.414 4 110 2.193 25 113 2.203 7 113 2.065 4 021 2.073 ＜1 021 2.015 4 202 2.024 6 202 1.847 5 024 1.856 2 024 1.805 16 018 1.818 8 018 1.787 21 116 1.797 10 116 1.780 3 009 1.795 5 009 1.567 4 211 1.573 2 211 1.545 7 122 1.550 4 122 1.465 4 214 1.472 4 214 1.444 4 208 1.452 4 208 1.389 4 300 1.394 2 300
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表 4 标准白云石、铁白云石晶胞参数(ICDD数据)
Table 4. Standard unit-cell parameters of dolomite and ankerite from ICDD
矿物种类 晶胞参数 a(Å) c(Å) V(Å3) 白云石(36-426) 4.809 0 16.020 0 320.88 铁白云石(41-586) 4.829 0 16.152 0 326.15
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表 5 微生物介导的白云石与标准白云石及铁白云石的晶胞参数比较
Table 5. Comparison of unit-cell parameters between dolomites and ankerite
米勒指数
(hkl)微生物介导白云石
d(hkl)Å白云石
d(hkl)Å铁白云石
d(hkl)Å方解石
d(hkl)Å102 3.71 3.69 3.70 3.86 110 2.40 2.41 2.41 2.49 122 1.55 1.54 1.55 1.60 104 2.94 2.89 2.90 3.03 注：微生物介导白云石数据源自 Vasconcelos et al.(1995) .
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