Coupling relationship between the stability of Li/Be complexes and Li/Be differential enrichment in granitic pegmatites—an experimental study

doi:10.13745/j.esf.sf.2023.5.3

Abstract

Abstract:

Pegmatite lithium (Li)-beryllium (Be) deposits are an important type of strategic Li-Be deposit. However, anatexis, on one hand, only produces a small amount of pegmatite-forming melts while Li/Be extraction efficiency for anatectic pegmatites is low; on the other hand, it is still controversial whether magmatic fractional crystallization results in high Li/Be enrichment in pegmatites and increased extraction efficiency. With the observation of fluid immiscibility in Li/Be-rich silica melt, it suggested that melt-fluid immiscibility may also lead to pegmatite formation. Current studies on the pegmatite Li-Be mineralization processes during the melt-fluid phase mainly focus on the whole-rock geochemical characteristics of granitic pegmatites, the in-situ geochemical changes of the rock-forming minerals (mica, quartz, feldspar, etc.) and ore minerals (beryl, etc.), and the mineralogical and geochemical characteristics of melt/fluid inclusions in petrogenic minerals, ore minerals, and accessory minerals (garnet, etc.). So far no obvious correlation has been found between the depositional age and the types of melt/fluid inclusions. To understand the mechanism of abnormal Li/Be enrichments in pegmatites it is key to study the distribution and stability of Li/Be complexes during the melt-fluid phase, however, the former study is scarce and the latter non-existent. In this study we investigated the effects of pH and calcium/aluminum additions on the stability of Li/Be complexes. We found that (1) the stability of Be complex was more affected by pH compared to Li complex; (2) under constant pH, the addition of aluminum promoted Be but hindered Li precipitations; and (3) the addition of calcium had less effect on Li than on Be precipitations. Future high-temperature, high-pressure experimental simulation studies should further enhance our understanding of the Li/Be enrichment processes and provide a geochemical basis for new Li/Be mineralization models based on the stability of Li/Be complexes.

Key words: Li-Be deposits, melt/fluid inclusions, stability of Li/Be complexes, episodic metallogenic process

CLC Number:

P571

HONG Tao, ZHAI Mingguo, WANG Yuejun, LIU Xingcheng, XU Xingwang, GAO Jun, HU Mingxi, MA Jing. Coupling relationship between the stability of Li/Be complexes and Li/Be differential enrichment in granitic pegmatites—an experimental study[J]. Earth Science Frontiers, 2023, 30(5): 93-105.

Figures/Tables 10

References 90

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产地	主矿物	子晶矿物组合	Be和Li₂O的质量分数/10^-6	文献来源
Beauvoir, France	花岗岩全岩		303±58(Be)	Charoy^[32]
实验室合成	无堇青石花岗岩		130(Be)	London和Evensen^[35]
Ehrenfriedersdorf, Germany	熔体包裹体		9 600(Be)	Webster等^[13]
Zinnwald, Germany	熔体包裹体		670(Be)	Webster等^[43]
Mt. Malosa	伟晶状石英中熔体包裹体		570±150(Be)	Zajacz等^[44]
Ehrenfriedersdorf, Erzgebirge, Germany	伟晶状石英中熔体包裹体	锂磷铝石+磷铍钙石+ 磷酸钠铍石+硼铍石	1 450(Be)	Thomas等^[41]
富Ta(Ta质量分数为2 000×10^-6~ 4 000×10^-6)细晶岩	实验熔体		10 000(Li₂O )	Linnen^[49]

产地	主矿物	子晶矿物组合	Be和Li₂O的质量分数/10^-6	文献来源
Beauvoir, France	花岗岩全岩		303±58(Be)	Charoy^[32]
实验室合成	无堇青石花岗岩		130(Be)	London和Evensen^[35]
Ehrenfriedersdorf, Germany	熔体包裹体		9 600(Be)	Webster等^[13]
Zinnwald, Germany	熔体包裹体		670(Be)	Webster等^[43]
Mt. Malosa	伟晶状石英中熔体包裹体		570±150(Be)	Zajacz等^[44]
Ehrenfriedersdorf, Erzgebirge, Germany	伟晶状石英中熔体包裹体	锂磷铝石+磷铍钙石+ 磷酸钠铍石+硼铍石	1 450(Be)	Thomas等^[41]
富Ta(Ta质量分数为2 000×10^-6~ 4 000×10^-6)细晶岩	实验熔体		10 000(Li₂O )	Linnen^[49]

铍质量的变化			锂质量的变化
控制沉淀时的pH值	制备K₃BeF₄溶液,换算出其中Be质量。 m₁(Be)/mg	沉淀物以Be(OH)₃为主,换算出其中Be质量。 m₂(Be)/mg	控制沉淀时的pH值	制备LiF溶液,换算出其中Li质量。 m₁(Li)/mg	沉淀物以Li₂CO₃为主,换算出其中Li质量。 m₂(Li)/mg
7	69	0	7	80	0
8	69	2.5	8	80	1.22
9	69	3.95	9	80	2.35
10	69	30.23	10	80	2.47
12	69	63.56	12	80	2.53

铍质量的变化			锂质量的变化
控制沉淀时的pH值	制备K₃BeF₄溶液,换算出其中Be质量。 m₁(Be)/mg	沉淀物以Be(OH)₃为主,换算出其中Be质量。 m₂(Be)/mg	控制沉淀时的pH值	制备LiF溶液,换算出其中Li质量。 m₁(Li)/mg	沉淀物以Li₂CO₃为主,换算出其中Li质量。 m₂(Li)/mg
7	69	0	7	80	0
8	69	2.5	8	80	1.22
9	69	3.95	9	80	2.35
10	69	30.23	10	80	2.47
12	69	63.56	12	80	2.53

铍质量的变化						锂质量的变化
制备K₃BeF₄溶液,换算出其中Be质量。 m₁(Be)/mg	加入不同量的CaCl₂,换算出其中Ca质量。 m₁(Ca)/mg	沉淀时的pH值	从K₃BeF₄及不同量的CaCl₂混合溶液中沉淀物以Be(OH)₂为主,换算出其中Be质量。 m₂(Be)/mg	从上列混合溶液中,沉淀出CaF₂,换算出其中Ca质量。 m₂(Ca)/mg		制备1 mol (锂辉石) LiAl(SiO₃)₂/ Li₂O·Al₂O₃·4SiO₂,换算出其中Li 质量。 m₁(Li)/mg		加入不同量的CaCO₃,换算出其中Ca质量。 m₃(Ca)/mg		沉淀时的pH值		从锂辉石及不同量的CaCO₃混合溶液中沉淀物以铝酸锂(LiAlO₂) 和硅酸钙为主,换算出其中Li 质量。 m₂(Li)/mg		从上列混合溶液中,沉淀出硅酸钙,换算出其中Ca质量。 m₄(Ca)/mg
69	35.7	7	2.7	31.23	20.8		32		7		11.1		30.2
69	71.4	7	4.68	64.01	20.8		73.2		7		13.5		60.1
69	107.1	7	7.92	102.24	20.8		103.2		7		28.2		100.2
69	142.8	7	9.9	136.02	20.8		144.2		7		37.9		116.2
69	178	7	14.78	170.8	20.8		166.5		7		44.3		144.2