地学前缘 ›› 2022, Vol. 29 ›› Issue (1): 81-92.DOI: 10.13745/j.esf.sf.2021.8.7
唐勇1(), 覃山县1,2, 赵景宇3, 吕正航1, 刘喜强1,2, 王宏1,2, 陈剑争1,2, 张辉1,*()
收稿日期:
2020-06-20
修回日期:
2021-01-22
出版日期:
2022-01-25
发布日期:
2022-02-22
通讯作者:
张辉
作者简介:
唐 勇(1980—),男,研究员,博士生导师,主要从事伟晶岩成矿与找矿研究。E-mail: tangyong@vip.gyig.ac.cn
基金资助:
TANG Yong1(), QIN Shanxian1,2, ZHAO Jingyu3, LÜ Zhenghang1, LIU Xiqiang1,2, WANG Hong1,2, CHEN Jianzheng1,2, ZHANG Hui1,*()
Received:
2020-06-20
Revised:
2021-01-22
Online:
2022-01-25
Published:
2022-02-22
Contact:
ZHANG Hui
摘要:
花岗伟晶岩型矿床是稀有金属矿床重要的类型之一。在花岗伟晶岩中,稀有金属元素Li、Be、Nb和Ta主要以独立矿物的形式存在,前人对稀有金属独立矿物在硅酸盐熔体中的溶解度及其影响因素展开了系统研究。本文综合分析了已有的实验数据,其结果表明,影响稀有金属独立矿物溶解度最为重要的2个参数是温度(T)和铝饱和指数(ASI)。因此本文建立了稀有金属独立矿物,尤其是铌锰矿和钽锰矿溶解度,与温度(T)和铝饱和指数(ASI)之间的定量关系:
lg [w(Li)/10-6]=-0.37×[1 000/(T/K)]+4.56,R2=0.44
lg [w(BeO)/10-6]=-4.21×[1 000/(T/K)]+6.86,R2=0.91
lg [Ksp(Nb)/(mg2·kg-2)]=-(2.86±0.14)×ASI(Mn+Li)-(4.95±0.31)×[1 000/(T/K)]+(4.20+0.28),R2=0.86
lg [Ksp(Ta)/(mg2·kg-2)]=-(2.46±0.11)×ASI(Mn+Li)-(4.86±0.30)×[1 000/(T/K)]+(4.00+0.30),R2=0.80
式中,温度T为热力学温度,ASI(Mn+Li)(ASI=Al2O3/(CaO+Na2O+K2O+Li2O+MnO),摩尔分数比)和T的适用范围分别为0.6~1.2和1 073~1 373 K的范围内。上述公式为估算硅酸盐熔体中稀有金属含量提供了便利,为量化花岗伟晶岩成矿模型提供了基础。
稀有金属独立矿物溶解度随温度降低和铝饱和指数的增加而急剧降低,因此,在岩浆演化过程中,由岩浆侵位、分离结晶以及流体作用等因素引起的岩浆温度降低和铝饱和指数的增加,是导致稀有金属独立矿物结晶的主要机制。
中图分类号:
唐勇, 覃山县, 赵景宇, 吕正航, 刘喜强, 王宏, 陈剑争, 张辉. 稀有金属矿物溶解度对花岗伟晶岩成矿作用的制约[J]. 地学前缘, 2022, 29(1): 81-92.
TANG Yong, QIN Shanxian, ZHAO Jingyu, LÜ Zhenghang, LIU Xiqiang, WANG Hong, CHEN Jianzheng, ZHANG Hui. Solubility of rare metals as a constraint on mineralization of granitic pegmatite[J]. Earth Science Frontiers, 2022, 29(1): 81-92.
图1 挥发组分对铌锰矿和钽锰矿溶解度的影响 (数据引自文献[10,12,14-15])
Fig.1 Effect of flux elements on the solubility of Mn-columbite and Mn-tantalite. Data adapted from [10,12,14-15].
图2 温度对稀有金属独立矿物溶解度的影响 (数据引自文献[10-13,15-21])
Fig.2 Effect of temperature on the solubility of independent rare-metal minerals. Data adapted from [10-13,15-21].
序号 | ASI | 矿物 | 等式 | R2 | 斜率 | H/(kJ·mol-1) |
---|---|---|---|---|---|---|
1 | 1.00 | 锂辉石 | lg [w(Li)/10-6]=-0.37×[1 000/(T/K)]+4.56 | 0.44 | 0.37 | 7.1 |
2 | 1.00 | 绿柱石 | lg [w(BeO)/10-6] =-2.75×[1 000/(T/K)]+5.89 | 0.95 | 3.32 | 63.6 |
3 | >1.00 | 绿柱石 | lg [w(BeO)/10-6] =-4.21×[1 000/(T/K)]+6.86 | 0.91 | 4.21 | 80.6 |
4 | 0.60 | 铌锰矿 | lg [ | 0.78 | 2.32 | 44.4 |
5 | 1.00 | 铌锰矿 | lg [ | 0.98 | 5.56 | 106.5 |
6 | 1.20 | 铌锰矿 | lg [ | 1.00 | 8.06 | 154.3 |
7 | 0.90 | 钽锰矿 | lg [ | 0.98 | 5.28 | 101.1 |
8 | 1.00 | 钽锰矿 | lg [ | 0.94 | 7.01 | 134.2 |
9 | 1.10 | 钽锰矿 | lg [ | 0.94 | 5.19 | 99.4 |
表1 温度对稀有金属矿物溶解度影响 (数据引自[10-13,15-21])
Table 1 Effect of temperature on solubility of rare metal minerals. Data adapted from [10-13,15-21].
序号 | ASI | 矿物 | 等式 | R2 | 斜率 | H/(kJ·mol-1) |
---|---|---|---|---|---|---|
1 | 1.00 | 锂辉石 | lg [w(Li)/10-6]=-0.37×[1 000/(T/K)]+4.56 | 0.44 | 0.37 | 7.1 |
2 | 1.00 | 绿柱石 | lg [w(BeO)/10-6] =-2.75×[1 000/(T/K)]+5.89 | 0.95 | 3.32 | 63.6 |
3 | >1.00 | 绿柱石 | lg [w(BeO)/10-6] =-4.21×[1 000/(T/K)]+6.86 | 0.91 | 4.21 | 80.6 |
4 | 0.60 | 铌锰矿 | lg [ | 0.78 | 2.32 | 44.4 |
5 | 1.00 | 铌锰矿 | lg [ | 0.98 | 5.56 | 106.5 |
6 | 1.20 | 铌锰矿 | lg [ | 1.00 | 8.06 | 154.3 |
7 | 0.90 | 钽锰矿 | lg [ | 0.98 | 5.28 | 101.1 |
8 | 1.00 | 钽锰矿 | lg [ | 0.94 | 7.01 | 134.2 |
9 | 1.10 | 钽锰矿 | lg [ | 0.94 | 5.19 | 99.4 |
图3 熔体组成(ASI)对绿柱石、铌锰矿和钽锰矿溶解度的影响 (数据引自文献[10-13,15-20,22])
Fig.3 Effect of melt composition (ASI) on the solubility of beryl, Mn-columbite and Mn-tantalite. Data adapted from [10-13,15-20,22].
图5 稀有金属元素溶解度-温度的关系图 a—甲基卡X03伟晶岩脉中Li2O含量最大为1.5%;b—伟晶岩中已知最低和平均Be含量分别为30×10-6和200×10-6;c,d—熔体MnO含量受锰铝榴石的控制,熔体中MnO含量与温度的关系[31]为:ln[MnO]=-9 747.4/(T/K)+5.24,T为热力学温度。Tanco伟晶岩全岩铌和钽的含量分别为56×10-6和300×10-6。
Fig.5 Temperature-solubility diagrams for Li, Be, Nb and Ta
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