硼同位素分馏的实验理论认识和矿床地球化学研究进展

doi:10.13745/j.esf.sf.2020.4.43

摘要/Abstract

摘要：

硼是一种中等挥发性元素,具有¹¹B和¹⁰B两个稳定同位素。两个同位素间高达10%的相对质量差使其在地质过程中引起高达-70‰至+75‰的硼同位素变化。硼在自然界主要与氧键合形成三配位(BO₃)和四配位(BO₄)结构,因而¹¹B和¹⁰B间同位素分馏主要受控于三配体(BO₃)和四面体(BO₄)间配分。本文综述了低温和高温地质过程的硼同位素分馏的理论和实验研究进展。在溶液中B(OH)₃和${B(OH)^{-}_{4}}$间硼同位素分馏受pH和热力学p-T条件控制,实验和理论表征获得常温常压条件下的B(OH)₃和$B(OH)^{-}_{4}$间同位素分馏系数(α_3-4)变化范围为1.019 4至1.033 3。低温条件下矿物(如碳酸盐、黏土矿物(蒙脱石和伊利石)、针铁矿、水锰矿、硼酸盐)与溶液间硼同位素分馏行为除了受p-T-pH影响外,矿物表面吸附引起的分馏效应十分显著。在中高温过程(蒙脱石伊利石化、富硼电气石和白云母矿物与热液流体,以及硅酸盐熔体与流体)中硼同位素分馏行为受到硼配位构型、化学成分以及物理化学条件的控制。随着硼同位素分馏机理研究的深入以及越来越完善的地质储库硼同位素端员特征表征,硼同位素地球化学指标可以灵敏示踪成矿物质来源、探究成矿作用与成因模式和重建成矿过程物理化学条件。目前矿床硼同位素地球化学研究的难点在于实现不同赋存相(如流体、矿物和熔体)中硼配位键合结构和硼同位素组成的精细化表征。

关键词: 硼同位素, 量子力学计算, 平衡/动力学同位素分馏, 电气石-云母, 矿床

Abstract:

Boron is a moderately volatile element with two stable isotopes ¹¹B and ¹⁰B. As much as 10% relative mass difference between the two isotopes leads to significant variation in boron isotopic composition from -70‰ to +75‰ in nature. Boron is always bound to oxygen forming tetrahedral (BO₄) and trigonal (BO₃) coordination structures. The isotope fractionation between¹⁰B and ¹¹B is mainly controlled by their partition between the two structures. In this study, we gave a comprehensive review on the advances in equilibrium fractionation of boron isotopes in various processes. In solution, the boron isotope fractionation factor between B(OH)₃ and ${B(OH)^{-}_{4}}$ (α_3-4) is controlled by pH and thermodynamic p-T conditions. At ambient conditions, the α_3-4 values ranged from 1.0194 to 1.0333 by experimental and theoretical approaches. In addition to p-T-pH controls, boron isotope fractionation, caused by mineral surface adsorption between minerals (carbonates, clay minerals (montmorillonite and illite), goethite, hydromanganese, borate, etc.) and solution, is significant at low temperature. In medium and high temperature processes, boron isotope fractionation during illitization of smectite, tourmaline and muscovite minerals and in hydrothermal fluids or silicate melts and fluids are controlled by boron coordination, chemical composition, and physicochemical conditions. With further understanding of boron isotope fractionation mechanisms in individual process and isotopic distribution in various geological reservoirs, boron isotopes may be considered as sensitive indices for tracing ore-forming material sources, exploring ore-forming processes and genesis models, as well as reconstructing physicochemical conditions during ore formation. To better constrain geological concerns using boron isotopes in ore deposit geochemistry, the remaining challenges are to achieve fine characterizations of boron coordination and isotopic compositions in different host phases, such as fluids, minerals and melts.

Key words: boron isotopes, quantum mechanics calculation, equilibrium/kinetic isotopic fractionation, tourmaline-mica, ore deposits

中图分类号:

P597.2

李银川, 董戈, 雷昉, 魏海珍. 硼同位素分馏的实验理论认识和矿床地球化学研究进展[J]. 地学前缘, 2020, 27(3): 14-28.

LI Yinchuan, DONG Ge, LEI Fang, WEI Haizhen. Experimental and theoretical understanding of boron isotope fractionation and advances in ore deposit geochemistry study[J]. Earth Science Frontiers, 2020, 27(3): 14-28.

图/表 8

表1 常温常压条件下溶液中B(OH)3和B(OH ) 4 -之间硼同位素分馏因子实验值和计算值

Table 1 Experimental and calculated boron isotopic fractionation factors between B(OH)3 and B(OH ) 4 - in aqueous solution at ambient condition

研究方法	α_3-4	参考文献
实验研究
合成海水实验(25 ℃)	1.027 2±0.000 6	[12]
纯水实验(25 ℃)	1.030 8±0.002 3
合成海水实验(25 ℃)	1.028 5±0.001 6	[13]
天然海水测量实验(25 ℃)	1.026±0.001	[14]
理论计算
实验光谱和力场模拟(26.8 ℃)	1.019 4	[15]
实验光谱和力场模拟(26.8 ℃)	1.017 6	[16]
从头算分子轨道理论(分子,25 ℃)	1.026	[17]
从头算分子轨道理论(海水,25 ℃)	1.027	[18]
从头算分子轨道理论(纯水,25 ℃)	1.025 5
密度泛函理论(水溶液,25 ℃)	1.028 5	[19]
密度泛函理论(水溶液,25 ℃)	1.033 3±0.001 3	[20]
校正的分子轨道理论(水溶液,25 ℃)	1.026~1.028
密度泛函理论(水溶液,25 ℃)	1.031	[21]

表2 矿物、熔体、流体、蒸汽体系的平衡硼浓度配分系数

Table 2 Boron equilibrium partition coefficients among different mineral, melt, fluid and steam systems

体系	T/℃	p/MPa	[B]配分系数	参考文献
流体-蒸汽	450	38.6~41.8	1.19~1.45	[25]
流体-蒸汽	400	23.4~27.9	1.09~2.3	[25]
黑云母-火山玻璃	755~820	150~180	0.011	[63]
黑云母-火山玻璃	750~800	100~150	0.004	[63]
黑云母-火山玻璃	850~880	100~200	0.008	[63]
方解石-流体	20	0.1	2.5~4.0	[33]
高镁方解石-流体	20	0.1	6.5~9.9	[33]
文石-流体	20	0.1	10.2~22.8	[33]
针铁矿表面-不同pH流体	25	0.1	6±0.8~39±1.1	[46]
水钠锰矿表面-不同pH流体	25	0.1	3±0.8~34±1.2	[46]
流体-玄武岩熔体	950~1 100	110~170	0.33~0.54	[4]
流体-流纹岩熔体	750~850	500	1.2	[4]
低盐度流体-细晶岩熔体	800	100	4.6±1.3	[65]
高盐度流体-细晶岩熔体	800	100	0.91±0.49	[65]
单斜辉石-流体	900	2 000	0.007 7±0.001 9~0.031±0.013	[66]
石榴石-流体	900	2 000	0.000 62±0.000 12	[66]
橄榄石-熔体	1 325~1 450	1 000~1 500	0.019~0.048	[67]
斜方辉石-熔体	1 450	1 000	0.027	[67]
单斜辉石-熔体	1 325	1 000	0.117	[67]
尖晶石-熔体	1 325	1 000	0.08	[67]
蒸汽-熔体	> 645	200	≥ 1	[68]

图1 花岗岩岩浆流体出溶对流体相、残余熔体和电气石B同位素组成的影响。上标Ⅲ和Ⅳ表示赋存相中硼的配位数(据文献[86]修改)

Fig.1 Schematic diagram showing predicted effect of fluid exsolution from granitic magma on boron isotopic compositions of fluid phase, residual melt, and tourmaline. Superscripts Ⅲ and Ⅳ indicate the boron coordination number for different phases. Modified from [86].

图2 热液流体与不同硼源岩石作用生成电气石δ11B值变化示意图(据文献[87]修改)

Fig.2 Schematic diagram showing changes of tourmaline δ11B value due to interactions between hydrothermal fluid and different boron source rocks.Modified from [87].

图3 不同地质体中硼同位素组成(据文献[86,93-98])

Fig.3 Boron isotopic compositions of different geological materials. Adapted from [86,93-98].

图4 不同类型母岩中电气石硼同位素组成及推测的硼源(据文献[100]修改) 绿色字体表示轻同位素的硼源,红色字体表示重同位素的硼源。

Fig.4 Boron isotopic compositions of tourmalines from different host-rocks (colored boxes) and various inferred boron source (grey bands). Label colors: Green—sources for lighter boron isotope;Red—sources for heavier boron isotope. Modified from [100].

图5 地球主要硅酸盐储库中B总量和同位素组成。硅酸盐地球(BSE)等于原始地幔(据文献[94]修改)

Fig.5 Geochemical budget of B in Earth's major silicate reservoirs. The Bulk Silicate Earth (BSE) equals the primitive mantle. Modified from [94].

图6 含电气石热液矿床构造背景示意图(据文献[126]修改)

Fig.6 Schematic diagram of tectonic settings of tourmaline-bearing hydrothermal ore deposits. Modified from [126].

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