磁铁矿LA-ICP-MS分析在矿床成因研究中的应用

doi:10.11867/j.issn.1001-8166.2017.03.0262

地球科学进展 ›› 2017, Vol. 32 ›› Issue (3): 262 -275. doi: 10.11867/j.issn.1001-8166.2017.03.0262

黄柯 ^1, ²(

), 朱明田 ¹, 张连昌 ^1, ^*(

), 李文君 ^1, ², 高炳宇 ¹

1. 中国科学院地质与地球物理研究所矿产资源研究重点实验室,北京 100029
2.中国科学院大学,北京 100049

收稿日期:2016-11-01 修回日期:2017-02-10 出版日期:2017-03-20
通讯作者: 张连昌 E-mail:huangke@mail.iggcas.ac.cn;lczhang@mail.iggcas.ac.cn
基金资助:
国家自然科学基金面上项目“内蒙古毕力赫单金斑岩型矿床成矿作用研究”(编号:41572073)资助

LA-ICP-MS Analysis of Magnetite and Application in Genesis of Mineral Deposit

Ke Huang ^1, ²( ), Mingtian Zhu ¹, Lianchang Zhang ^1, ^*( ), Wenjun Li ^1, ², Bingyu Gao ¹

1.Key Laboratory of Mineral Resources, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing 100029, China
2.University of Chinese Academy of Sciences, Beijing 100049, China

Received:2016-11-01 Revised:2017-02-10 Online:2017-03-20 Published:2017-03-20
Contact: Lianchang Zhang E-mail:huangke@mail.iggcas.ac.cn;lczhang@mail.iggcas.ac.cn
About author:
First author:Huang Ke(1992-),male,Quxian County,Sichuan Province,Master student.Research areas include hydrothermal ore deposit.E-mail:huangke@mail.iggcas.ac.cn
Supported by:
Project supported by the National Natural Science Foundation of China“Ore-forming processes of the Bilihe gold-only porphyry deposit, Inner Mongolia”(No.41572073)

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激光剥蚀电感耦合等离子体质谱(LA-ICP-MS),由于其原位、实时、低检测限、高空间分辨率等优点,在矿物原位微量元素分析方面具有独特的优势。磁铁矿作为多种矿床和岩石中的常见矿物,其化学组成一直是国内外学者关注的焦点。而大量的研究表明,在磁铁矿LA-ICP-MS分析过程中,基体效应不明显,一般采用富铁硅酸盐玻璃作为标样,就能够取得较为准确的结果。因此近年来磁铁矿原位微量元素研究进展迅速,并在反演成岩成矿条件、辅助判别矿床类型和间接指导找矿勘探等方面显示出广泛的应用前景。通过总结25个不同类型岩浆和热液矿床中磁铁矿微量元素数据,与前人在矿床类型判别上的研究进行了一定的对比,发现常用的磁铁矿判别图解可以用来区分多种不同类型的矿床,但是已经划分出的分类边界可能需要进一步细化和严格验证,并且事先仔细的岩相学观察是数据解释的重要基础。另外,通过磁铁矿微量元素分配对岩浆和热液过程一系列复杂物理化学条件(熔/流体成分、温度、冷却速率、压力、氧逸度、硫逸度和二氧化硅活度等)的响应进行了一定探讨。在岩浆阶段,磁铁矿成分与熔体组成及分异演化密切相关;而热液阶段,流体性质的变化也会显著改变磁铁矿的化学成分。并且后期流体的改造或者磁铁矿的亚固相再平衡作用会对磁铁矿的成因鉴别产生严重干扰。综述了近年来LA-ICP-MS在磁铁矿微量元素分析方面的发展以及在矿床学领域的重要应用,以期对成矿作用和成矿过程研究提供新的思路和方向。

关键词: 微量元素, 磁铁矿, LA-ICP-MS, 成矿过程

Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS) is well characterized by the in-situ, real time, lower limit of detection and high space resolution, etc. Therefore, it is more excellent in the analysis of trace element for varied minerals in comparison to other micro-zone analysis technologies. Magnetite as a common mineral from different deposits and rocks has been focused on chemical compositions by researchers worldwide. In fact, as the insignificant matrix effect for most elements in magnetite, analysis results could be calculated effectively against Fe-rich silicate glass as the reference material. Therefore, researches on trace element distribution of magnetite have been developed rapidly in recent years, and it has a wide application prospect in reflecting the condition of ore-forming, discriminating different deposit types and indicating prospecting exploration. Comparing varied previous discrimination diagrams about magnetite via collecting trace element data from available literatures based on 25 deposits, we found that there was an urgent need for further detailing and reexamining the boundary of fields representing different genetic types, and it was vital for interpreting the data through carefully petrographical observation before analysis. In addition, we discussed several complex physicochemical factors, which would influence the element concentration of magmatite in igneous and hydrothermal processes, such as melt/fluid composition, temperature, cooling rate, pressure, oxygen fugacity, sulfur fugacity and silica activity. In magma stage, Magnetite’s components are closely related to melts composition and differentiation, while fluid features would also significantly change magnetie's components. Furthermore, there is serious interference for discriminating the genesis of magnetite because of late stage fluids and equilibrium again in subsolidus condition. This paper reviewed the developments of trace elements analysis by LA-ICP-MS and important applications about magnetite in mineral deposit so that unique thoughts for the research on mineralization and ore-forming processes could be obtained.

Key words: Trace elements, Magnetite, LA-ICP-MS, Ore-forming process.

中图分类号:

P578.46

图1 尖晶石族矿物间成分转换示意图 ^{[

15
]}
粗线连接的2个矿物表示可以形成完全固溶体,细线代表两者能形成有限固溶体

Fig.1 Schematic representation of composition transformation among the spinel group minerals ^{[

15
]}
Complete solid solution is shown by thick lines and limited solid solution is represented as thin lines between minerals

图2 不同配位数下Fe离子与其他常见阳离子的有效离子半径和化合价 ^{[

36
,

37
]}

Fig.2 Two diagrams that show the relationship between iron ion and other common cations with different ionic radiuses and cation charges in various coordination polyhedron ^{[

36
,

37
]}

图3 不同氧逸度—硫逸度条件下Fe赋存状态的变化 ^{[

37
,

43
]}
(a)Fe-Si-O体系氧化还原缓冲对与log fO ₂- T关系图(HM:赤铁矿—磁铁矿,FMQ:铁橄榄石—磁铁矿—石英,MW:磁铁矿—方铁矿,IW:单质铁—方铁矿,IM:单质铁—磁铁矿,QIF:石英—单质铁—铁橄榄石);(b)Fe-O-S体系随氧逸度—硫逸度( fO ₂— fS ₂)变化相图

Fig.3 The transformation of iron occurrence varies with oxygen and sulfur fugacity ^{[

37
,

43
]}
(a)log fO ₂- T diagram showing relevant buffers for the Fe-Si-O system(HM: hematite-magnetite,FMQ:fayalite-magnetite-quartz,MW:magnetite-wüstite, IW: iron-wüstite, IM:iron-magnetite, QIF: quartz-iron-fayalite);(b)Schematic phase diagram for the system Fe-O-S in fO ₂- fS ₂ space

图4 磁铁矿成因判别三角图 ^{[

47
~

49
]}
(a)I.副矿物型,II.岩浆熔离钛磁铁矿型,III.火山岩型,IV.接触交代型,V.矽卡岩型,VI.沉积变质型;(b)I.沉积变质—接触交代磁铁矿,IIa.超基性—基性—中性岩浆磁铁矿,IIb.酸性—碱性岩浆磁铁矿;(c)I.花岗岩区(酸性岩浆岩—伟晶岩),II.玄武岩区(拉斑玄武岩等),III.辉长岩区(辉长岩—橄榄岩、二长岩、斜长岩—副矿物及铁矿石),IV.橄榄岩区(橄榄岩、纯橄榄岩、辉岩等—副矿物及铁矿石),V ₁.角闪岩区(包括单斜辉石岩),V ₂.闪长岩区,VI.金伯利岩区,VII.热液型及钙矽卡岩型(虚线以上主要为深成热液型,以下为热液型及矽卡岩型),VIII.热液型及镁矽卡岩型(深成热液型,部分为热液交代型),IX.沉积变质,热液叠加型,X.碳酸盐岩区(X ₁与基性岩有关,X ₂与围岩交代有关),XI.过渡区

Fig.4 Genetic discriminant ternary diagram of magnetite related major elements ^{[

47
~

49
]}
(a)I. Accessory mineral type,II. Magma immiscible titanomagnetite type,III. Volcanic type,IV. Contact metasomatic type,V. Skarn type,VI. Sedimentary metamorphic type;(b)I. Sedimentary metamorphic-contact metasomatic magnetite,IIa. Ultrabasic-basic-intermediate igneous magnetite,IIb. Acid-alkaline igneous magnetite;(c)I. Granite field(acidic rock,pegmatite),II. Basalt field(tholeiite, etc.),III. Gabbro field (gabbro,peridotite,monzonite,anorthosite-accessory mineral and iron ore),IV. Peridotite field(peridotite,dunite,pyroxenite, etc.accessory mineral and iron ore),V ₁. Amphibolite filed(including clinopyroxenite),V ₂. Diorite field,VI. Kimberlite field,VII. Hydrothermal type and calc-skarn type(hypogene hypothermal type above dash line,and hydrothermal plus skarn type below dash line),VIII. Hydrothermal type and magnesium skarn type(including hypothermal type and hydrothermal metasomatic type,partly),IX. Sedimentary metamorphic,hydrothermal overlapping type,X. Carbonatite field(including X ₁ area related basic rock and X ₂ area related wall rock alteration),XI. Transitional field

图5 判别不同类型矿床的Al/Co-Sn/Ga图解(数据来自参考文献[27,33,34,55~63])

Fig.5 The Sn/Ga vs. Al/Co diagram to distinguish magnetite from different deposit types(data from references [27,33,34,55~63])

表1 发育磁铁矿的代表性岩浆和热液矿床

Table 1 Representative magmatic and hydrothermal deposits that yield commonly magnetite

矿床类型	代表性矿床	矿床位置	分析方法	参考文献
岩浆铜—镍—铂族元素矿床(Cu-Ni-PGEs)	新疆黄山东Ni-Cu矿床	中国西北部东天山造山带	LA-ICP-MS	[33]
岩浆铜—镍—铂族元素矿床(Cu-Ni-PGEs)	Lac des Iles铂族元素矿床	加拿大Ontario地区	LA-ICP-MS	[56]
岩浆Fe-Ti-V矿床	太和、攀枝花、红格、安益、白马矿床	中国西南部	LA-ICP-MS	[57]
斑岩型矿床	Island Copper(Cu-Mo-Au),Pine(Cu-Au),Copper Mountain(Cu-Au)、Mount Polley(Cu-Au),Endako (Mo)	加拿大Cordillera地区	LA-ICP-MS	[58]
矽卡岩型矿床	Argo/Iron Hill(矽卡岩型Fe矿)、Port Renfrew(块状—似层状矿体)	加拿大Cordillera地区	LA-ICP-MS	[58]
	广东怀集藤铁Fe矿	华南地区连阳岩体南缘鱼鹿岩株内外接触带	LA-ICP-MS	[59]
	凤凰山Cu-Fe-Au矿床	中国东部铜陵地区	LA-ICP-MS	[34]
基律纳型(Kiruna)	El Laco	智利	LA-ICP-MS	[60]
IOCG	拉拉铜矿	康滇Fe-Cu多金属成矿省	LA-ICP-MS	[61]
IOCG	Ernest Henry	澳大利亚西部Cloncurry地区	LA-ICP-MS	[27]
VMS	Izok Lake Halfmile Lake	加拿大Nunavut地区加拿大New Brunswick地区	LA-ICP-MS, EPMA	[55]
条带状铁建造(BIF)	K和A矿床	澳大利亚西部Koolyanobbing矿区	LA-ICP-MS	[62]
条带状铁建造(BIF)	Hayot,Rainy,Wishart矿床	加拿大Labrador地区Sokoman铁建造	LA-ICP-MS	[63]

表1 发育磁铁矿的代表性岩浆和热液矿床

Table 1 Representative magmatic and hydrothermal deposits that yield commonly magnetite

矿床类型	代表性矿床	矿床位置	分析方法	参考文献
岩浆铜—镍—铂族元素矿床(Cu-Ni-PGEs)	新疆黄山东Ni-Cu矿床	中国西北部东天山造山带	LA-ICP-MS	[33]
岩浆铜—镍—铂族元素矿床(Cu-Ni-PGEs)	Lac des Iles铂族元素矿床	加拿大Ontario地区	LA-ICP-MS	[56]
岩浆Fe-Ti-V矿床	太和、攀枝花、红格、安益、白马矿床	中国西南部	LA-ICP-MS	[57]
斑岩型矿床	Island Copper(Cu-Mo-Au),Pine(Cu-Au),Copper Mountain(Cu-Au)、Mount Polley(Cu-Au),Endako (Mo)	加拿大Cordillera地区	LA-ICP-MS	[58]
矽卡岩型矿床	Argo/Iron Hill(矽卡岩型Fe矿)、Port Renfrew(块状—似层状矿体)	加拿大Cordillera地区	LA-ICP-MS	[58]
	广东怀集藤铁Fe矿	华南地区连阳岩体南缘鱼鹿岩株内外接触带	LA-ICP-MS	[59]
	凤凰山Cu-Fe-Au矿床	中国东部铜陵地区	LA-ICP-MS	[34]
基律纳型(Kiruna)	El Laco	智利	LA-ICP-MS	[60]
IOCG	拉拉铜矿	康滇Fe-Cu多金属成矿省	LA-ICP-MS	[61]
IOCG	Ernest Henry	澳大利亚西部Cloncurry地区	LA-ICP-MS	[27]
VMS	Izok Lake Halfmile Lake	加拿大Nunavut地区加拿大New Brunswick地区	LA-ICP-MS, EPMA	[55]
条带状铁建造(BIF)	K和A矿床	澳大利亚西部Koolyanobbing矿区	LA-ICP-MS	[62]
条带状铁建造(BIF)	Hayot,Rainy,Wishart矿床	加拿大Labrador地区Sokoman铁建造	LA-ICP-MS	[63]

图6 基于磁铁矿成分的多种矿床类型判别图(底图据参考文献[15,37])

Fig.6 Discrimination diagram of different deposit fields based on magnetite compositions (base maps are from references[15,37])

图7 区分岩浆和热液磁铁矿的Ni/Cr-Ti图解(分界线据参考文献[52])

Fig.7 The Ni/Cr vs Ti diagram to distinguish magmatic and hydrothermal magnetite (boundary refers to reference[52])

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