Experimental and theoretical understanding of boron isotope fractionation and advances in ore deposit geochemistry study

doi:10.13745/j.esf.sf.2020.4.43

Abstract

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

CLC Number:

P597.2

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.

Figures/Tables 8

References 128

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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]

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]

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]

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]