Formation, Modification and Analytical Techniques of Melt Inclusion, and Their Applications in Economic Geology
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摘要: 熔体包裹体研究不仅广泛应用于火山岩和部分侵入岩系统，而且因其具有可以保存岩浆初始挥发分和金属组成的优势，近来也逐步应用于矿床学领域.在介绍熔体包裹体形成机制和捕获后成分改造的基础上，简要归纳了目前常用的熔体包裹体分析方法，以斑岩型Cu-(Mo-Au)和斑岩型Mo成矿系统为例，重点介绍熔体包裹体在矿床学领域的应用，包括成矿金属和挥发分含量的测定，以及熔体-流体分配系数测定等方面.然而，熔体包裹体在捕获后均会受到不同程度的成分改造，且对于大多数造岩矿物内的熔体包裹体，其成分改造的具体机制仍不明了，因此在实际应用过程中，需要对其组成进行具体分析和甄别.随着分析技术的改善和提高，熔体包裹体捕获后具体成分改造机制有待进一步查明，进而推动熔体包裹体的应用.现阶段熔体包裹体在斑岩型Cu-(Mo-Au)和斑岩型Mo成矿岩浆系统的成功应用表明，相比全岩地球化学研究，熔体包裹体已成为研究成矿岩浆体系内成矿金属和挥发分演化的重要手段.
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关键词:
- 熔体包裹体 /
- 斑岩型Cu-(Mo-Au)矿床 /
- 斑岩型Mo矿床 /
- 电子探针 /
- 二次离子质谱 /
- 激光剥蚀电感耦合等离子体质谱
Abstract: Melt inclusion has been widely used in the research of volcanic and some magmatic systems, and now gradually applied to economic geology because of its absolute advantage over whole-rock analysis in preserving the primary metal and volatile composition of ore-forming magmas. In this paper, we firstly present melt inclusion formation and post-entrapment modification on its composition, then summarize the commonly used analytical techniques for melt inclusion studies, and finally take porphyry Cu-(Mo-Au) and porphyry Mo systems as examples to introduce its applications in economic geology, including determination of ore-forming metals, volatile composition, and fluid-melt partition coefficients. Considering the facts that most melt inclusions have been modified to a certain degrees after their entrapment, and that the modification mechanism for most rock-forming minerals has not been well understood, attention has to be paid to the melt inclusion data and associated interpretation.With the improvement of analytical methods, such ambiguous post-entrapment modification mechanism may be resolved in the near future, and in turn it can promote the applications of melt inclusion. The successful applications of melt inclusion in porphyry Cu-(Mo-Au) and porphyry Mo systems confirm that melt inclusion has been an important and powerful tool in studying ore-forming metals and volatile evolution in ore-forming magma systems in comparison with whole-rock study. -
图 1 石英内不同类型熔体包裹体形成示意(a)及部分典型熔体包裹体显微照片(b~d)
a.熔体包裹体形成示意(据Audétat and Lowenstern, 2014)，其中熔体包裹体A~D均为原生，E为假次生，F为次生，包裹体C和D代表捕获其他结晶相、不混溶熔体或流体相(白色部分)；b.石英内随机分布原生熔体包裹体(MI)；c.捕获锆石的玻璃质熔体包裹体，该情况较少见；d.石英内沿生长带分布熔体包裹体(MI)
Fig. 1. Schematic view showing the formation of different types of melt inclusions within quartz crystal (a), and microphotographs of typical melt inclusions (b-d)
图 2 典型筛状结构斜长石(a)和单斜辉石(b)内部熔体包裹体(MI)显微照片
Fig. 2. Microphotographs of melt inclusions within sieve-textured plagioclase (a) and clinopyroxene (b)
图 3 石英内不同程度结晶(a~e)和局部破裂(f)熔体包裹体显微照片
a.玻璃质熔体包裹体；b、c.部分结晶熔体包裹体；d.细结晶熔体包裹体，其中箭头指示包裹体经历侧壁结晶之前的原始轮廓；e.粗结晶熔体包裹体；f.局部破裂熔体包裹体
Fig. 3. Microphotographs of melt inclusions with variable crystallinity (a-e) and partly cracked melt inclusion (f)
图 4 使用高压容器(Ar气压为2 GPa)加热均一石英内结晶熔体包裹体的前后变化
Fig. 4. Changes in the appearance of crystallized melt inclusions during stepwise homogenization at 2 GPa Ar confining pressure
图 5 LA-ICP-MS分析橄榄石内结晶熔体包裹体剥蚀示意和对应信号
a.橄榄石内结晶熔体包裹体；b.激光剥蚀完整熔体包裹体示意(据Pettke, 2006)；c.对应的LA-ICP-MS信号
Fig. 5. Schematic diagram of LA-ICP-MS analysis of a crystallized melt inclusion within olivine crystal, and corresponding transient signals
图 6 矿化与非矿化岩浆系统镁铁质端元熔体包裹体Cu(a)和S(b)含量对比
Fig. 6. Comparison of Cu (a) and S (b) concentrations in mafic melt inclusions from mineralized and barren systems
图 7 斑岩型Mo矿床、弱矿化和未矿化岩浆体系熔体包裹体Mo含量对比
据Audétat(2015)；Henderson和Silver Creek数据引自Zhang and Audétat(2017b)
Fig. 7. Comparison of Mo concentrations from porphyry Mo-mineralized, sub-economically Mo-mineralized and barren systems
图 8 来自不同构造环境和斑岩型Mo矿床岩浆体系中流纹质熔体包裹体Rb与F含量变化关系
据Audétat(2015)；Pine Grove数据引自Lowenstern(1994)；Henderson和Silver Creek数据引自Zhang and Audétat(2017b)
Fig. 8. Rb vs. F diagram for rhyolitic melt inclusions from different tectonic settings and from porphyry Mo-mineralized systems
表 1 常用熔体包裹体成分分析技术方法的特点及优缺点对比
Table 1. Comparison among different characteristics of commonly used methods for analyzing melt inclusion composition, and their corresponding advantages and disadvantages
分析方法 包裹体要求 分析元素/同位素 空间分辨率(μm) 检测限(10-6) 优点 缺点 EPMA 均一、暴露至表面 主量和部分微量元素 1~20 500 非破坏性、同一包裹体可多次分析 分析元素少；Na丢失现象；样品准备工作繁琐；不适用于无法完全均一的包裹体 SIMS 均一、暴露至表面 微量元素、挥发分、稳定同位素、Pb同位素 10~30 ＜1 对同一包裹体进行多种分析 分析效率低；样品准备工作繁琐；不适用于无法完全均一的包裹体 LA-ICP-MS 包裹体埋深不能过大 主微量和稀土元素、Sr和Pb同位素 10~100 ＜1 无需均一化；分析元素范围广、效率高；样品准备工作简单 同一包裹体无法重复分析；无法测定挥发分；内标选择引入误差 注：据文献Kent (2008)； Mason et al.(2008) ；Audétat and Lowenstern (2014)修改.
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表 2 斑岩型Mo成矿岩浆与未矿化岩浆Mo流体/熔体分配系数对比
Table 2. Comparison of fluid-melt partition coefficients of Mo from porphyry Mo-mineralized and barren magmas
岩体 样品 流体盐度(% NaClequiv.) 流体均一温度(℃) 流体包裹体Mo含量(10-6) 熔体包裹体Mo含量(10-6) DMo流体/熔体 数据来源 矿化 Cave Peak MC2A-GT 18.0 550~600 127±4 7.3±1.5 17.4±3.6 Audétat(2010) Cave Peak MC2A-GZ 19.0 550~600 106±11 5.3±1.7 19.8±6.7 Audétat(2010) 未矿化 Stronghold Stro 1A 5.9 412 46±9 3.2±2.2 14.4±10.3 Audétat et al.(2008) Rito del Medio Rtio5 last gz 4.9 420 133±6 9.3±2.4 14.3±3.7 Zajacz et al.(2008) Rito del Medio Rito5 2nd last gz 4.5 425 168±20 7.4±2.0 22.7±6.7 Zajacz et al.(2008) Huangshan HS8 4.7 389 75±14 3.6±0.5 20.8±4.8 未发表数据 注：据Audétat(2015)修改；流体盐度为质量百分含量.
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表 3 不同斑岩型Mo成矿岩浆物理化学性质对比
Table 3. Comparison of physical and chemical properties of ore-forming magmas from porphyry Mo systems
Climax Henderson Pine Grove Silver Creek Mo(10-6) 5~7 10~15 ~2 3~4 F(%) 3.10~4.50 0.45~0.56 0.28~0.38 0.25~0.32 H2O(%) ~6.0 5.2~7.2 6.0~8.0 5.8~9.4 T(℃)1 710~730 740~780 710~720 780~800 log η(Pa·s)2 4.8~4.9 4.4~4.9 4.5~5.1 3.5~4.4 注：据Zhang and Audétat(2017b)修改；1.锆石饱和温度；2.岩浆粘度；F和H2O为质量百分含量.
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