川西冕宁木落寨碳酸岩型稀土矿床流体演化对成矿的制约:来自包裹体和稳定同位素的证据
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摘要
木落寨稀土矿床位于青藏高原东部,扬子克拉通西南缘,属于典型的碳酸岩型稀土矿床。与其他成矿过程复杂的碳酸岩型稀土矿床相比,该矿床具有完整而连续的流体演化过程,且几乎不受热液蚀变和后期构造-岩浆事件的影响,因此是研究碳酸岩型稀土矿床成矿过程的理想对象。本次研究结合详细的1∶5000矿区岩性-构造-蚀变-矿化野外地质调查和流体包裹体研究,将矿床形成过程划分为三期,即岩浆期、热液期和表生期。热液期作为主要的成矿期,又可细分为热液早阶段、热液中阶段和热液晚阶段三个阶段。对热液不同阶段的重晶石、萤石、石英和氟碳铈矿的流体包裹体研究表明,主要分为以下6类:(1)熔体(M类)包裹体;(2)熔流包裹体;(3)富CO_2包裹体(WC类);(4)含子矿物富CO_2包裹体(SC类);(5)含子矿物水溶液三相包裹体(S类);(6)气液两相包裹体(W类)。热液早阶段为岩浆-热液过渡阶段,以粗粒萤石和重晶石为特征,发育熔融和熔流包裹体,指示成矿流体来自岩浆出溶。WC、SC和S类包裹体主要在热液中阶段石英和萤石中而W类包裹体大部分存在于热液晚阶段氟碳铈矿中。WC类包裹体具有不同的CO_2充填度,表明热液中阶段成矿流体发生不混溶作用。结合WC类包裹体端元组成的显微测温结果和等容线法,模拟计算出不混溶作用发生的温度为280～320℃之间,压力为120～180MPa,盐度范围较大,为2. 4%～42. 4%Na Cleqv。热液成矿期晚阶段氟碳铈矿中的W类包裹体具有稳定的气液比,说明成矿环境较均匀,其测温结果显示大规模稀土矿化主要发生在200～260℃之间,压力<200bars,盐度为6. 5%～11. 2%Na Cleqv。激光拉曼结果显示SC和S类包裹体中的子晶主要为重晶石、天青石和无水芒硝等硫酸盐,指示成矿流体富集Na~+、Ca~(2+)、K~+、Sr~(2+)、Ba~(2+)、SO_4~(2-)、F~-和Cl~-离子。成矿流体δD和δ~(18)O同位素组成分别为-96. 5‰～-50. 1‰和0. 9‰～6. 4‰,与区域上其他碳酸岩型稀土矿流体同位素组成相似,指示流成矿流体出溶过程中经历自岩浆脱气做作用,且晚阶段有大气降水加入。热液成矿期中阶段硫化物和硫酸盐的δ34SV-CDT分别为集中在-6. 10‰～-4. 77‰和4. 33‰～4. 90‰,与区域其他稀土矿床硫同位素值吻合,反应幔源岩浆硫特征。硫酸盐和硫化物的硫平衡分馏计算结果为16. 7‰～25. 1‰,远大于二者差值(9. 1‰～11. 0‰),显示成矿晚阶段为开放系统。以上研究结果和实验岩石学共同指示木落寨矿床稀土元素在热液中主要以[REE(SO4)2]-和[REECl]2+形式迁移,不混溶作用是流体演化的重要过程,提供成矿所需CO_2,而成矿流体冷却和大气降水混入致使络合物分解被认为是热液晚阶段稀土矿物大规模沉淀的主要机制。
The Muluozhai rare earth element( REE) deposit located in eastern Tibetan Plateau and southwestern Yangtze,is the typical carbonatite-related REE deposit. Compared with other carbonatite-related REE deposits with complicated mineralization processes,the Muluozhai REE deposit has a completed and continuous fluid evolution process and is almost unaffected by hydrothermal alteration and late tectono-magmatic events. Therefore,it is an ideal target for understanding the mineralization process of REE deposits. Based on the detail geological investigation of the 1∶5000 petrology-structure-alteration-mineralization mapping and the study of fluid inclusions,three periods are recognized,namely:( 1) magmatic period;( 2) hydrothermal period and( 3) supergene period.The hydrothermal period is the main mineralization period with divided into early,middle and late stages. The results of study on fluid inclusions in fluorite,quartz and bastnsite from different hydrothermal stages show that six types are recognized,as followed:( 1)melt inclusion( M type);( 2) melt-fluid inclusion( ML type);( 3) CO_2-rich aqueous fluid inclusion( WC type);( 4) solid-bearing CO_2-rich fluid inclusion( SC type);( 5) solid-bearing aqueous fluid inclusion( S type); and( 6) aqueous-rich fluid inclusion( W type). The early hydrothermal stage is transition from magmatic to hydrothermal process. This stage is characterized by coarse-grained fluorite and barite and host M and ML types inclusions,implying that the ore-forming fluid exsolved from magma. WC,SC and S types inclusions are dominant in the fluorite and quartz from the middle hydrothermal stage whereas the W type inclusions are abundant in bastnsite from the late hydrothermal stage. Generally,the WC type inclusions with various carbonic filling degrees are interpreted as the immiscibility took place in the middle hydrothermal stage. Based on the microthermometric and isochoric results of end members of WC type inclusions,immiscibility is constrained at the temperature of 280 ～ 320℃,pressure of 120 ～ 180 MPa and salinities range from2. 4% to 42. 4% Na Cleqv. In the late hydrothermal stage,the W type inclusions in bastnsite have the constant vapor/liquid ratios,indicating that mineralization occurs in the relatively homogeneous environment. Meanwhile,the microthermometric results of W type inclusions show the mineralization occurred at the temperature of 200 ～ 260℃,pressure less than 200 bars and salinities ranges from6. 5% to 11. 2% Na Cleqv. The results of laser Raman spectrum show the solids in SC and S types inclusions are consist of barite,celestine,mirabilite and glaserite,demonstrating that the ore-forming fluid is rich in Na~+,Ca~(2+),K~+,Sr~(2+),Ba~(2+),SO_4~(2-),F~- as well as Cl~-. In addition,the δD and δ~(18) O values of ore-forming fluid range of-96. 5‰ ～-50. 1‰ and 0. 9% ～ 6. 4‰,respectively,corresponding to those in other REE deposits from the same belt. This implies the ore-forming fluid might initially derived from the degasification of magma and mixed with meteoric water in the late. The δ34 SV-CDTvalues between sulfide and sulphate in the Muluozhai deposit are concentrated in-6. 10‰ ～-4. 77‰ and 4. 33‰ ～ 4. 90‰,respectively,which are similar with those in the other REE deposits from the same region and show the characteristics of mantle. The calculation of sulfur equilibrium fractionation between sulphate and sulfide varies from 16. 7‰ to 25. 1‰,which are more than the differential values( 9. 1‰ ～ 11. 0‰) between them,showing mineralization belongs to an open system. Based on the above results and experimental petrology,REEs migrate as [REE( SO_4)_2]~- and [REECl]~(2+) complexes in the hydrothermal fluid. Immiscibility is an important process to support CO_2 for mineralization.But fluid cooling and mixing with meteoric water are regarded as the main mechanism of mineralization by decomposition of complexes.
The Muluozhai rare earth element( REE) deposit located in eastern Tibetan Plateau and southwestern Yangtze,is the typical carbonatite-related REE deposit. Compared with other carbonatite-related REE deposits with complicated mineralization processes,the Muluozhai REE deposit has a completed and continuous fluid evolution process and is almost unaffected by hydrothermal alteration and late tectono-magmatic events. Therefore,it is an ideal target for understanding the mineralization process of REE deposits. Based on the detail geological investigation of the 1∶5000 petrology-structure-alteration-mineralization mapping and the study of fluid inclusions,three periods are recognized,namely:( 1) magmatic period;( 2) hydrothermal period and( 3) supergene period.The hydrothermal period is the main mineralization period with divided into early,middle and late stages. The results of study on fluid inclusions in fluorite,quartz and bastnsite from different hydrothermal stages show that six types are recognized,as followed:( 1)melt inclusion( M type);( 2) melt-fluid inclusion( ML type);( 3) CO_2-rich aqueous fluid inclusion( WC type);( 4) solid-bearing CO_2-rich fluid inclusion( SC type);( 5) solid-bearing aqueous fluid inclusion( S type); and( 6) aqueous-rich fluid inclusion( W type). The early hydrothermal stage is transition from magmatic to hydrothermal process. This stage is characterized by coarse-grained fluorite and barite and host M and ML types inclusions,implying that the ore-forming fluid exsolved from magma. WC,SC and S types inclusions are dominant in the fluorite and quartz from the middle hydrothermal stage whereas the W type inclusions are abundant in bastnsite from the late hydrothermal stage. Generally,the WC type inclusions with various carbonic filling degrees are interpreted as the immiscibility took place in the middle hydrothermal stage. Based on the microthermometric and isochoric results of end members of WC type inclusions,immiscibility is constrained at the temperature of 280 ～ 320℃,pressure of 120 ～ 180 MPa and salinities range from2. 4% to 42. 4% Na Cleqv. In the late hydrothermal stage,the W type inclusions in bastnsite have the constant vapor/liquid ratios,indicating that mineralization occurs in the relatively homogeneous environment. Meanwhile,the microthermometric results of W type inclusions show the mineralization occurred at the temperature of 200 ～ 260℃,pressure less than 200 bars and salinities ranges from6. 5% to 11. 2% Na Cleqv. The results of laser Raman spectrum show the solids in SC and S types inclusions are consist of barite,celestine,mirabilite and glaserite,demonstrating that the ore-forming fluid is rich in Na~+,Ca~(2+),K~+,Sr~(2+),Ba~(2+),SO_4~(2-),F~- as well as Cl~-. In addition,the δD and δ~(18) O values of ore-forming fluid range of-96. 5‰ ～-50. 1‰ and 0. 9% ～ 6. 4‰,respectively,corresponding to those in other REE deposits from the same belt. This implies the ore-forming fluid might initially derived from the degasification of magma and mixed with meteoric water in the late. The δ34 SV-CDTvalues between sulfide and sulphate in the Muluozhai deposit are concentrated in-6. 10‰ ～-4. 77‰ and 4. 33‰ ～ 4. 90‰,respectively,which are similar with those in the other REE deposits from the same region and show the characteristics of mantle. The calculation of sulfur equilibrium fractionation between sulphate and sulfide varies from 16. 7‰ to 25. 1‰,which are more than the differential values( 9. 1‰ ～ 11. 0‰) between them,showing mineralization belongs to an open system. Based on the above results and experimental petrology,REEs migrate as [REE( SO_4)_2]~- and [REECl]~(2+) complexes in the hydrothermal fluid. Immiscibility is an important process to support CO_2 for mineralization.But fluid cooling and mixing with meteoric water are regarded as the main mechanism of mineralization by decomposition of complexes.
引文
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