云南大丫口祖母绿颜色环带成因对多阶段成矿的指示意义

doi:10.13745/j.esf.sf.2020.5.48

摘要/Abstract

摘要：

云南大丫口祖母绿常出现颜色环带,且伴随明显成分变化,而目前颜色环带的成因仍存争议,相关的多阶段成矿假说尚缺少明确证据。文章通过电子探针和激光剥蚀电感耦合等离子质谱仪对大丫口祖母绿的颜色环带及黑色矿物包裹体进行主微量元素成分分析,并对不同类型岩脉祖母绿中流体包裹体进行显微测温分析,进而探讨祖母绿颜色环带成因与多阶段成矿的联系。成分测试结果表明,从浅绿白核部至绿色边部,V(970×10^-6→10 077×10^-6)、Rb(9.6×10^-6→27.4×10^-6)、Cs(535×10^-6→3 108×10^-6)、Fe(1 376×10^-6→2 199×10^-6)和Ga(4×10^-6→14.7×10^-6)等微量元素的含量急剧增加。结合绿色晶体边部中同生黑色富钒电气石包裹体的分布,有力证明了大丫口祖母绿颜色分带的形成与晶体的多阶段成矿有关。流体包裹体测试结果表明,含矿长石-方解石脉、含矿石英脉和伟晶岩-变粒岩接触带中矿物的流体包裹体盐度范围分别为3.39%~10.36%(NaCl_eq)、5.71%~12.29%(NaCl_eq)和8%~18.72%(NaCl_eq),指示了伟晶岩脉中祖母绿的多阶段结晶,且表明随结晶阶段演变,成矿流体的盐度逐渐升高。同时,成矿流体盐度升高也是晚期云英岩化阶段致色元素含量剧增的原因。

关键词: 云南祖母绿, 主微量成分分析, 流体包裹体, 颜色环带成因, 多阶段成矿

Abstract:

Color zonation with obvious composition variation often appear in emeralds from Dayakou, Yunnan Province, China. However, the origin of color zonation is still controversial, and there has been no reliable evidence for the related multistage mineralization hypothesis. In this study, we analyzed the main and trace elemental signatures of the Dayakou emerald with obvious color zonation by electron microprobe (EMP) and laser-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). We also carried out microthermal analysis of fluid inclusions hosted within emerald and other associate minerals from different types of veins. The composition results showed that the trace elemental contents in emerald increased sharply from the light greenish white core to the green rim, yielding V((970-10077)×10^-6), Rb((9.6-27.4)×10^-6), Cs((535-3108)×10^-6), Fe((1376-2199)×10^-6) and Ga((4-14.7)×10^-6); and the syngenetic black inclusions which only occur at the green crystalline rim were proved to be V-rich intermediate oxy-schorl-dravite. The above evidence strongly suggests that color zonation are formed from multistage crystalline mineralization. Furthermore, the microthermal analysis results showed that salinities of fluid inclusions hosted within minerals from the feldspar-calcite and quartz veins and pegmatite-granofel contact zones were 3.39%-10.36%, 5.71%-12.29% and 8%-18.72%(NaCl_eq), respectively, again indicating different mineralization stages in pegmatite veins and suggesting increasing parent fluid salinity with evolution of the mineralization stage. And the considerable variation of V concentration is also caused by increasing salinity at the greisenization stage.

Key words: Yunnan emerald, major and trace elemental analysis, fluid inclusions, origin of color zonation, multistage mineralization

中图分类号:

余晓艳, 郑育宇, 张婷雅, 郭鸿舒, 龙政宇, 万佳鑫, 张存. 云南大丫口祖母绿颜色环带成因对多阶段成矿的指示意义[J]. 地学前缘, 2020, 27(5): 116-125.

YU Xiaoyan, ZHENG Yuyu, ZHANG Tingya, GUO Hongshu, LONG Zhengyu, WAN Jiaxin, ZHANG Cun. The genesis of color zonation of emerald from Dayakou, Yunnan Province: implication for multi-stage mineralization[J]. Earth Science Frontiers, 2020, 27(5): 116-125.

图/表 8

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测试矿物	测试点		w_B/%
测试矿物	测试点		SiO₂		TiO₂		Al₂O₃		Sc₂O₃		V₂O₃		Cr₂O₃		BeO		MgO^a		CaO		MnO		FeO		NiO		CoO		Na₂O		K₂O		Li₂O		Cs₂O		H₂O^b		Total
祖母绿 (边部→ 核部→ 边部)	YE-6-1	66.14		0.06		15.04		bdl		0.84		0.02		13.65		0.64		0.03		bdl		0.69		bdl		bdl		0.95		0.04		0.07		0.40		2.16		98.57
	YE-6-2	66.83		0.04		15.86		bdl		1.31		0.07		13.83		0.75		bdl		bdl		0.43		bdl		bdl		0.82		0.03		0.05		0.20		2.08		100.22
	YE-6-3	67.22		bdl		16.51		0.04		0.8		0.01		13.85		0.78		bdl		bdl		0.45		0.01		0.03		0.83		0.01		0.09		0.15		2.08		100.78
	YE-6-4	66.94		bdl		16.94		0.01		0.22		bdl		13.80		0.78		0.01		bdl		0.3		bdl		bdl		0.83		0.03		0.08		0.07		2.08		100.01
	YE-6-5	66.85		bdl		16.92		bdl		0.27		bdl		13.75		0.72		bdl		0.03		0.28		bdl		0.02		0.78		0.01		0.10		0.11		2.06		99.84
	YE-6-6	66.82		bdl		16.84		0.01		0.24		0.01		13.76		0.66		bdl		bdl		0.27		bdl		0.06		0.76		0.02		0.09		0.12		2.04		99.66
	YE-6-7	67.43		0.06		16.13		0.02		1.02		0.03		13.94		0.65		bdl		bdl		0.45		0.01		bdl		0.68		0.03		0.06		0.22		1.97		100.73
	YE-6-8	67.04		bdl		14.88		bdl		0.93		0.03		13.96		nd		0.04		bdl		0.64		0.04		bdl		0.76		0.02		bdl		0.31		2.04		98.65
测试矿物	测试点		单位原子数/apfu
测试矿物	测试点		Si⁴⁺		Al³⁺		Ti⁴⁺		Sc³⁺		V³⁺		Cr³⁺		Mg²⁺		Mn²⁺		Fe²⁺		Ni²⁺		Co²⁺		Y tot		Y_sub(RD)				^OR²⁺		Be²⁺		Ca²⁺		Na⁺		K⁺		Cs⁺	^CA⁺
祖母绿 (边部→ 核部→ 边部)	YE-6-1	6		1.608		0.004		bdl		0.061		0.001		0.087		bdl		0.052		bdl		bdl		1.814		0.206(11.40%)				0.139		2.975		0.003		0.167		0.005		0.016		0.213
	YE-6-2	6		1.678		0.003		bdl		0.094		0.005		0.100		bdl		0.032		bdl		bdl		1.912		0.234(12.20%)				0.132		2.982		bdl		0.143		0.003		0.008		0.172
	YE-6-3	6		1.737		bdl		0.003		0.057		0.001		0.104		bdl		0.034		0.001		0.002		1.939		0.202(10.40%)				0.141		2.968		bdl		0.144		0.001		0.006		0.183
	YE-6-4	6		1.790		bdl		0.001		0.016		bdl		0.104		bdl		0.022		bdl		bdl		1.933		0.143(7.40%)				0.126		2.971		0.001		0.144		0.003		0.003		0.179
	YE-6-5	6		1.790		bdl		bdl		0.019		bdl		0.096		0.002		0.021		bdl		0.001		1.929		0.139(7.20%)				0.120		2.964		bdl		0.136		0.001		0.004		0.177
	YE-6-6	6		1.782		bdl		0.001		0.017		0.001		0.088		bdl		0.020		bdl		0.004		1.913		0.131(6.90%)				0.112		2.967		bdl		0.132		0.002		0.005		0.172
	YE-6-7	6		1.692		0.004		0.002		0.073		0.002		0.086		bdl		0.033		0.001		bdl		1.893		0.201(10.60%)				0.120		2.979		bdl		0.117		0.003		0.008		0.149
	YE-6-8	6		1.570		bdl		bdl		0.067		0.002		bdl		bdl		0.048		0.003		bdl		1.690		0.120(7.10%)				0.051		3.000		0.004		0.132		0.002		0.012		0.146
测试矿物	测试点		w_B/%
测试矿物	测试点		SiO₂		TiO₂		Al₂O₃		Sc₂O₃		V₂O₃		Cr₂O₃		MgO		CaO		MnO		FeO		NiO		CoO		Na₂O		K₂O		Cs₂O		H₂O		B₂O₃		Total
电气石	T-1	38.23		0		31.19		0		3.38		0.06		5.39		0.31		0.08		7.33		0.04		0.02		2.08		0.02		0.01		2.99		10.94		102.07
	T-2	37.58		0.09		28.48		0		3.55		0.09		1.51		1.18		0.03		7.13		0.02		0.05		2.34		0.05		0		2.91		10.75		95.76
	T-3	37.9		0.09		29.41		0		2.92		0.03		1.49		0.89		0.07		6.75		0.02		0		2.60		0.06		0		2.93		10.84		96.00
	T-4	37.46		0.06		27.61		0		3.87		0.11		6.78		1.32		0.10		7.36		0.03		0.03		2.33		0.23		0		3.14		10.72		101.15
测试矿物	测试点		单位原子数/apfu
测试矿物	测试点		B³⁺		^TSi⁴⁺		^ZAl³⁺		^ZV³⁺		^ZCr³⁺		^ZMg²⁺		^YAl³⁺		^YTi⁴⁺		^YV³⁺		^YCr³⁺		^YMg²⁺		^YMn²⁺		^YFe²⁺		^YNi²⁺		^YCo²⁺		^XCa²⁺		^XNa⁺		^XK⁺		^VOH		^WOH	^WO
电气石	T-1	2.965		6		5.770		0.222		0.008		0		0		0		0.203		0		1.262		0.010		0.962		0.005		0.002		0.052		0.634		0.005		3		0.136		0.864
	T-2	2.869		6		5.359		0.455		0.011		0.175		0		0.011		0		0		0.184		0.004		0.952		0.003		0.006		0.202		0.725		0.009		3		0.097		0.903
	T-3	2.867		6		5.487		0.371		0.004		0.137		0		0.011		0		0		0.215		0.009		0.894		0.002		0		0.150		0.798		0.012		3		0.091		0.909
	T-4	2.959		6		5.213		0.497		0.014		0.277		0		0.007		0		0		1.342		0.014		0.986		0.004		0.004		0.226		0.723		0.047		3		0.353		0.647

测试矿物	测试点		w_B/%
测试矿物	测试点		SiO₂		TiO₂		Al₂O₃		Sc₂O₃		V₂O₃		Cr₂O₃		BeO		MgO^a		CaO		MnO		FeO		NiO		CoO		Na₂O		K₂O		Li₂O		Cs₂O		H₂O^b		Total
祖母绿 (边部→ 核部→ 边部)	YE-6-1	66.14		0.06		15.04		bdl		0.84		0.02		13.65		0.64		0.03		bdl		0.69		bdl		bdl		0.95		0.04		0.07		0.40		2.16		98.57
	YE-6-2	66.83		0.04		15.86		bdl		1.31		0.07		13.83		0.75		bdl		bdl		0.43		bdl		bdl		0.82		0.03		0.05		0.20		2.08		100.22
	YE-6-3	67.22		bdl		16.51		0.04		0.8		0.01		13.85		0.78		bdl		bdl		0.45		0.01		0.03		0.83		0.01		0.09		0.15		2.08		100.78
	YE-6-4	66.94		bdl		16.94		0.01		0.22		bdl		13.80		0.78		0.01		bdl		0.3		bdl		bdl		0.83		0.03		0.08		0.07		2.08		100.01
	YE-6-5	66.85		bdl		16.92		bdl		0.27		bdl		13.75		0.72		bdl		0.03		0.28		bdl		0.02		0.78		0.01		0.10		0.11		2.06		99.84
	YE-6-6	66.82		bdl		16.84		0.01		0.24		0.01		13.76		0.66		bdl		bdl		0.27		bdl		0.06		0.76		0.02		0.09		0.12		2.04		99.66
	YE-6-7	67.43		0.06		16.13		0.02		1.02		0.03		13.94		0.65		bdl		bdl		0.45		0.01		bdl		0.68		0.03		0.06		0.22		1.97		100.73
	YE-6-8	67.04		bdl		14.88		bdl		0.93		0.03		13.96		nd		0.04		bdl		0.64		0.04		bdl		0.76		0.02		bdl		0.31		2.04		98.65
测试矿物	测试点		单位原子数/apfu
测试矿物	测试点		Si⁴⁺		Al³⁺		Ti⁴⁺		Sc³⁺		V³⁺		Cr³⁺		Mg²⁺		Mn²⁺		Fe²⁺		Ni²⁺		Co²⁺		Y tot		Y_sub(RD)				^OR²⁺		Be²⁺		Ca²⁺		Na⁺		K⁺		Cs⁺	^CA⁺
祖母绿 (边部→ 核部→ 边部)	YE-6-1	6		1.608		0.004		bdl		0.061		0.001		0.087		bdl		0.052		bdl		bdl		1.814		0.206(11.40%)				0.139		2.975		0.003		0.167		0.005		0.016		0.213
	YE-6-2	6		1.678		0.003		bdl		0.094		0.005		0.100		bdl		0.032		bdl		bdl		1.912		0.234(12.20%)				0.132		2.982		bdl		0.143		0.003		0.008		0.172
	YE-6-3	6		1.737		bdl		0.003		0.057		0.001		0.104		bdl		0.034		0.001		0.002		1.939		0.202(10.40%)				0.141		2.968		bdl		0.144		0.001		0.006		0.183
	YE-6-4	6		1.790		bdl		0.001		0.016		bdl		0.104		bdl		0.022		bdl		bdl		1.933		0.143(7.40%)				0.126		2.971		0.001		0.144		0.003		0.003		0.179
	YE-6-5	6		1.790		bdl		bdl		0.019		bdl		0.096		0.002		0.021		bdl		0.001		1.929		0.139(7.20%)				0.120		2.964		bdl		0.136		0.001		0.004		0.177
	YE-6-6	6		1.782		bdl		0.001		0.017		0.001		0.088		bdl		0.020		bdl		0.004		1.913		0.131(6.90%)				0.112		2.967		bdl		0.132		0.002		0.005		0.172
	YE-6-7	6		1.692		0.004		0.002		0.073		0.002		0.086		bdl		0.033		0.001		bdl		1.893		0.201(10.60%)				0.120		2.979		bdl		0.117		0.003		0.008		0.149
	YE-6-8	6		1.570		bdl		bdl		0.067		0.002		bdl		bdl		0.048		0.003		bdl		1.690		0.120(7.10%)				0.051		3.000		0.004		0.132		0.002		0.012		0.146
测试矿物	测试点		w_B/%
测试矿物	测试点		SiO₂		TiO₂		Al₂O₃		Sc₂O₃		V₂O₃		Cr₂O₃		MgO		CaO		MnO		FeO		NiO		CoO		Na₂O		K₂O		Cs₂O		H₂O		B₂O₃		Total
电气石	T-1	38.23		0		31.19		0		3.38		0.06		5.39		0.31		0.08		7.33		0.04		0.02		2.08		0.02		0.01		2.99		10.94		102.07
	T-2	37.58		0.09		28.48		0		3.55		0.09		1.51		1.18		0.03		7.13		0.02		0.05		2.34		0.05		0		2.91		10.75		95.76
	T-3	37.9		0.09		29.41		0		2.92		0.03		1.49		0.89		0.07		6.75		0.02		0		2.60		0.06		0		2.93		10.84		96.00
	T-4	37.46		0.06		27.61		0		3.87		0.11		6.78		1.32		0.10		7.36		0.03		0.03		2.33		0.23		0		3.14		10.72		101.15
测试矿物	测试点		单位原子数/apfu
测试矿物	测试点		B³⁺		^TSi⁴⁺		^ZAl³⁺		^ZV³⁺		^ZCr³⁺		^ZMg²⁺		^YAl³⁺		^YTi⁴⁺		^YV³⁺		^YCr³⁺		^YMg²⁺		^YMn²⁺		^YFe²⁺		^YNi²⁺		^YCo²⁺		^XCa²⁺		^XNa⁺		^XK⁺		^VOH		^WOH	^WO
电气石	T-1	2.965		6		5.770		0.222		0.008		0		0		0		0.203		0		1.262		0.010		0.962		0.005		0.002		0.052		0.634		0.005		3		0.136		0.864
	T-2	2.869		6		5.359		0.455		0.011		0.175		0		0.011		0		0		0.184		0.004		0.952		0.003		0.006		0.202		0.725		0.009		3		0.097		0.903
	T-3	2.867		6		5.487		0.371		0.004		0.137		0		0.011		0		0		0.215		0.009		0.894		0.002		0		0.150		0.798		0.012		3		0.091		0.909
	T-4	2.959		6		5.213		0.497		0.014		0.277		0		0.007		0		0		1.342		0.014		0.986		0.004		0.004		0.226		0.723		0.047		3		0.353		0.647

测试点 (边→核→边)		w_B/10^-6
测试点 (边→核→边)		Li	B	Na		Mg		P		K		Ca		Sc		Ti		V		Cr		Mn		Fe		Zn	Ga
YE-6-1		306	2.9	6 998		3 850		68		26.6		bdl		147		55.6		8 960		13		55.7		2 043		104	14.7
YE-6-2		237	9.6	7 067		4 504		90		42.3		bdl		100		54.8		10 077		2.2		59.5		2 069		51.1	11.3
YE-6-3		426	5.7	8 544		4 672		68		bdl		bdl		31.9		52.9		1 810		6.2		25.2		1 425		38.7	5.2
YE-6-4		394	4.3	8 021		4 714		61		15.8		bdl		15.8		56.4		970		5.8		24		1 376		48.2	4
YE-6-5		471	5.9	7 928		4 321		67		22.4		bdl		32.1		46.2		2 104		5.3		29.9		1 481		60.3	6.3
YE-6-6		410	9.1	7 474		3 949		80		11.9		bdl		52.4		44.3		2 696		9.8		32.6		1 401		67.9	11.3
YE-6-7		268	bdl	6 737		3 917		118		bdl		bdl		70.9		122		3 243		4.7		55.6		2 199		56.3	11.5
测试点 (边→核→边)	w_B/10^-6
测试点 (边→核→边)	As		Rb		Sr		Y		Zr		Sn		Cs		Ba		Hf		W		Bi		Pb		Th		U
YE-6-1	19.8		24.1		bdl		bdl		0.091		2.63		3 108		0.9		0.084		2		0.32		2.4		bdl		0.075
YE-6-2	bdl		26.2		0.4		bdl		0.052		1.04		2 190		bdl		bdl		0.1		bdl		0.2		bdl		bdl
YE-6-3	bdl		10.3		0.1		bdl		0.158		0.12		647		bdl		0.055		0.1		0.01		0.1		bdl		bdl
YE-6-4	19.7		9.6		0.3		bdl		0.124		1.63		535		bdl		bdl		1.6		0.15		10.1		bdl		0.071
YE-6-5	3.8		12.2		0.5		bdl		0.19		0.41		664		bdl		0.024		0.2		0.09		0.3		bdl		0.009
YE-6-6	5.3		12.9		1.3		bdl		bdl		1.4		653		3.1		bdl		bdl		bdl		0.7		bdl		0.022
YE-6-7	bdl		27.4		bdl		bdl		0.648		1.96		1 392		1		0.078		bdl		bdl		0.4		bdl		bdl

测试点 (边→核→边)		w_B/10^-6
测试点 (边→核→边)		Li	B	Na		Mg		P		K		Ca		Sc		Ti		V		Cr		Mn		Fe		Zn	Ga
YE-6-1		306	2.9	6 998		3 850		68		26.6		bdl		147		55.6		8 960		13		55.7		2 043		104	14.7
YE-6-2		237	9.6	7 067		4 504		90		42.3		bdl		100		54.8		10 077		2.2		59.5		2 069		51.1	11.3
YE-6-3		426	5.7	8 544		4 672		68		bdl		bdl		31.9		52.9		1 810		6.2		25.2		1 425		38.7	5.2
YE-6-4		394	4.3	8 021		4 714		61		15.8		bdl		15.8		56.4		970		5.8		24		1 376		48.2	4
YE-6-5		471	5.9	7 928		4 321		67		22.4		bdl		32.1		46.2		2 104		5.3		29.9		1 481		60.3	6.3
YE-6-6		410	9.1	7 474		3 949		80		11.9		bdl		52.4		44.3		2 696		9.8		32.6		1 401		67.9	11.3
YE-6-7		268	bdl	6 737		3 917		118		bdl		bdl		70.9		122		3 243		4.7		55.6		2 199		56.3	11.5
测试点 (边→核→边)	w_B/10^-6
测试点 (边→核→边)	As		Rb		Sr		Y		Zr		Sn		Cs		Ba		Hf		W		Bi		Pb		Th		U
YE-6-1	19.8		24.1		bdl		bdl		0.091		2.63		3 108		0.9		0.084		2		0.32		2.4		bdl		0.075
YE-6-2	bdl		26.2		0.4		bdl		0.052		1.04		2 190		bdl		bdl		0.1		bdl		0.2		bdl		bdl
YE-6-3	bdl		10.3		0.1		bdl		0.158		0.12		647		bdl		0.055		0.1		0.01		0.1		bdl		bdl
YE-6-4	19.7		9.6		0.3		bdl		0.124		1.63		535		bdl		bdl		1.6		0.15		10.1		bdl		0.071
YE-6-5	3.8		12.2		0.5		bdl		0.19		0.41		664		bdl		0.024		0.2		0.09		0.3		bdl		0.009
YE-6-6	5.3		12.9		1.3		bdl		bdl		1.4		653		3.1		bdl		bdl		bdl		0.7		bdl		0.022
YE-6-7	bdl		27.4		bdl		bdl		0.648		1.96		1 392		1		0.078		bdl		bdl		0.4		bdl		bdl

矿脉类型	主矿物	包裹体类型	数量	完全均一温度/℃	盐度 w(NaCl_eq)/%	均一相态	资料来源
长石- 方解石脉 (YN-1)	长石	富液两相	6	230~284	3.55~3.71	液相	本文
	祖母绿	富液两相	39	232~294	4.18~9.86	液相
	方解石	富液两相	21	246~289	3.39~10.36	液相
石英脉 (YN-2)	祖母绿	富液两相	41	299~349	5.71~10.73	液相
石英脉 (YN-2)	石英	富液两相	32	249~415	6.88~12.29	液相
伟晶岩- 围岩接触带 (YN-3)	方解石	富液两相	21	223~263	11.22~11.93	液相
	石英	富液两相	22	266~282	8~15.96	液相
	祖母绿	富液两相	31	227~345	9.08~18.72	液相
伟晶岩脉	祖母绿等	富液两相		256~282	8~11	液相	文献[24]
石英脉	祖母绿等	富液两相		250	13~18	液相
伟晶岩脉	祖母绿等	富液两相		210~323	5~12	液相
石英脉	祖母绿等	富液两相		216~327	13~18	液相	文献[25]
接触带	祖母绿等	富液两相			8~14	液相	文献[25]
伟晶岩脉	祖母绿等	富液两相		204~280	0~5.5	液相	文献[18]
石英脉	祖母绿等	富液两相			5.5~9	液相	文献[18]
伟晶岩脉	祖母绿等	富液两相		231~332	3.87~8.14	液相	文献[26]