赣中大王山钨钼多金属矿集区辉钼矿微量元素地球化学特征
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摘要
为厘清大王山钨钼多金属矿集区成矿流体性质和成矿物质来源,以矿床(点)中与黑钨矿共生的辉钼矿为研究对象,利用ICP-MS分析方法,展开稀土元素和微量元素地球化学研究。结果显示,辉钼矿中稀土元素含量较低(ΣREE=60.8×10~(-6)~92.19×10~(-6)),轻稀土元素(LREE)富集(LREE/HREE=15.50~36.84,平均为26.53),轻重稀土分异程度较弱((La/Yb)N=1.10~10.37,平均为4.35),辉钼矿稀土元素具有Ce负异常(δCe=0.21~0.44)和强烈的Eu亏损(δEu=0.01~0.03)现象,δSm与δCe呈负相关关系,ΣREE与δCe具有正相关性,指示其成矿条件为较高温的还原环境。微量元素多以非类质同象的机械混合或流体包裹体的形式存在,富集Cu,W,Bi,Pb等,除瑶蓝窝矿点的Nb/La>1外,其他矿床(点)的Nb/La,Hf/Sm,Th/La均<1,表明成矿流体富Cl。通过REE vs La/Yb图解可以看出辉钼矿与赋矿花岗岩投点范围集中,具有壳幔混合的同源性。综合前人对研究区硫化矿硫同位素特征的研究,结合La vs La/Sm图解,暗示中生代辉钼矿可能有一个共同的富集成矿元素的幔源区。大王山钨钼多金属矿集区的岩浆-流体在深部可能经历了两个主要演化过程:(1)幔源成矿物质与赋矿围岩岩浆在深部发生了充分的混合作用;(2)赋矿岩浆在演化后期发生了液态不混溶作用。
ICP-MS analysis is used for the geochemical study of rare earth elements and trace elements of the molybdenite associated with the ore deposit in the Dawangshan Tungsten-Molybdenum polymetallic ore concentration area,so as to clarify the ore-forming fluid properties and oreforming material sources.It shows that the molybdenite is poor in content of rare earth elements(ΣREE=60.8×10~(-6)~92.19×10~(-6)),rich in light rare earth elements((La/Yb)N=1.10~10.37,average 4.35),and the light and heavy rare earth elements are less well differentiated with negative Ce anomaly(δCe=0.21~0.44)and strong depletion of Eu(δEu=0.01~0.03).There is a negative correlation betweenδSm andδCe,and a positive correlation betweenΣREE andδCe,a condition of higher temperature and reducing environment.Most of the trace elements exist in the form of mechanical mixing of non-isomorphic or fluid inclusions,enriched in Cu,W,Bi,Pb,etc,Nb/La,Hf/Sm,Th/La<1 in most of the ore occurrences except Yaolanwo ore occurrence(Nb/La>1),indication of enrichment of Cl in the ore-forming fluid.REE vs La/Yb diagram shows that the molybdenite and ore-dressing granite have a wide range of plotting points and have the homology of crust-mantle mixing.Based on previous studies on the sulfur isotopic characteristics of sulphide ores in the study area and the combination of the La vs.La/Sm diagrams,it is considered that the Mesozoic molybdenite may have a common mantl-derived region rich in ore-forming elements.The magmatic fluid in the Dawangshan Tungsten-Molybdenum ore district experienced two major evolution processes in the deep:(1)the mantle source metallogenic material and the ore-bearing porphyry magmatism fully mixed in the deep;(2)liquid immiscibility effect occurred in the late stage of magma mineralization evolution.
ICP-MS analysis is used for the geochemical study of rare earth elements and trace elements of the molybdenite associated with the ore deposit in the Dawangshan Tungsten-Molybdenum polymetallic ore concentration area,so as to clarify the ore-forming fluid properties and oreforming material sources.It shows that the molybdenite is poor in content of rare earth elements(ΣREE=60.8×10~(-6)~92.19×10~(-6)),rich in light rare earth elements((La/Yb)N=1.10~10.37,average 4.35),and the light and heavy rare earth elements are less well differentiated with negative Ce anomaly(δCe=0.21~0.44)and strong depletion of Eu(δEu=0.01~0.03).There is a negative correlation betweenδSm andδCe,and a positive correlation betweenΣREE andδCe,a condition of higher temperature and reducing environment.Most of the trace elements exist in the form of mechanical mixing of non-isomorphic or fluid inclusions,enriched in Cu,W,Bi,Pb,etc,Nb/La,Hf/Sm,Th/La<1 in most of the ore occurrences except Yaolanwo ore occurrence(Nb/La>1),indication of enrichment of Cl in the ore-forming fluid.REE vs La/Yb diagram shows that the molybdenite and ore-dressing granite have a wide range of plotting points and have the homology of crust-mantle mixing.Based on previous studies on the sulfur isotopic characteristics of sulphide ores in the study area and the combination of the La vs.La/Sm diagrams,it is considered that the Mesozoic molybdenite may have a common mantl-derived region rich in ore-forming elements.The magmatic fluid in the Dawangshan Tungsten-Molybdenum ore district experienced two major evolution processes in the deep:(1)the mantle source metallogenic material and the ore-bearing porphyry magmatism fully mixed in the deep;(2)liquid immiscibility effect occurred in the late stage of magma mineralization evolution.
引文
[1]杨庆坤,宣璞琰,张小亮,等.赣中大王山钨多金属矿床流体包裹体及H-O-S同位素特征[J].地质科学,2017,52(4):1 282-1 296.
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[4]应立娟,唐菊兴,王登红,等.西藏甲玛铜多金属矿床矽卡岩中辉钼矿铼-锇同位素定年及其成矿意义[J].岩矿测试,2009,28(3):265-268.
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[7]刘晓文,李泽琴,王奖臻,等.扬子西南缘拉拉IOCG矿床辉钼矿微量元素地球化学特征[J].矿物岩石地球化学通报,2017,36(6):1 056-1 062.
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[15]黄凡,王登红,曾载淋,等.赣南园岭寨大型钼矿岩石地球化学、成岩成矿年代学及其地质意义[J].大地构造与成矿学,2012,36(3):363-376.
[16]郑大中,郑若锋.稀土元素的迁移形式富集机理初探[J].化工矿产地质,2003,25(4):219-228.
[17]丁振举,刘丛强,姚书振,等.东沟坝多金属矿床矿质来源的稀土元素地球化学限制[J].吉林大学学报(地球科学版),2003,33(4):437-442.
[18]李光来.赣南及邻区燕山期花岗岩演化与钨成矿作用[D].南京:南京大学,2011.
[19]王登红,李超,陈郑辉,等.辉钼矿在矿床学研究中的新用途(I):稀土元素示踪[J].吉林大学学报(地球科学版),2012,42(6):1 647-1 655.
[20]Mao J W,Zhang X Y,Zhang Z C,et al.Temporo-Spatial Distribution and Evolution of Ore Deposits in the West Sector of the Northern Qilian Mountains[J].Acta Geologica Sinica(English Edition),1999,73(2):230-241
[21]黄典豪,吴澄宇,杜安道,等.东秦岭地区钼矿床的铼-锇同位素年龄及其意义[J].矿床地质,1994,13(3):221-230.
[22]李红艳,毛景文,孙亚利,等.柿竹园钨多金属矿床的Re-Os同位素等时线年龄研究[J].地质论评,1994,42(3):261-267.
[23]赵海香,戴宝章,李斌,等.小秦岭车仓峪钼矿成因研究:辉钼矿Re-Os年龄及黄铁矿微量元素制约[J].岩石学报,2015,31(3):784-790.
[24]倪智勇,李诺,张辉,等.河南大湖金钼矿床成矿物质来源的锶钕铅同位素约束[J].岩石学报,2009,25(11):2 823-2 832.
[25]Roser B P,Korsch R J.Provenance signatures of sandstone-mudstone suits determined using discriminant function analysis of major-element data[J].Chemical Geology,1988,67(1):119-139.
[26]李顺庭,王京彬,祝新友,等.湖南瑶岗仙钨多金属矿床辉钼矿Re-Os同位素定年和硫同位素分析及其地质意义[J].现代地质,2011,25(2):228-235.
[27]李闫华,鄢云飞,谭俊,等.稀土元素在矿床学研究中的应用[J].地质找矿论丛,2007,22(4):294-298.
[28]Florian K,Carsten M,Jonas T,et al.Accurate stable tungsten isotope measurements of natural samples using a180 W-183 W double-spike Original Research[J].Chemical Geology,2018,476:407-417.
[29]周云飞,徐九华,单立华,等.新疆巴里坤小加山钨矿地质特征与成因[J].地质通报,2016,35(12):2 121-2 132.
[30]Deng X H,Chen Y J,Santoshd M,et al.U-Pb zircon,Re-Os molybdenite geochronology and Rb-Sr geochemistry from the Xiaobaishitou W(Mo)deposit:Implications for Triassic tectonic setting in eastern Tianshan,NW China[J].Ore Geology Reviews,2017,80:332-351.
[31]Pan X F,Hou Z Q,Li Y,et al.Dating the giant Zhuxi W-Cu deposit(Taqian-Fuchun Ore Belt)in South China using molybdenite Re-Os and muscovite Ar-Ar system[J].Ore Geology Reviews,2017,86:719-733.
[2]周家云,郑荣才,朱志敏,等.拉拉铜矿黄铁矿微量元素地球化学特征及其成因意义[J].矿物岩石,2008,28(3):64-71.
[3]黄凡,王登红,陈毓川,等.中国内生钼矿床辉钼矿的微量元素特征研究[J].矿床地质,2014,33(6):1 193-1 212.
[4]应立娟,唐菊兴,王登红,等.西藏甲玛铜多金属矿床矽卡岩中辉钼矿铼-锇同位素定年及其成矿意义[J].岩矿测试,2009,28(3):265-268.
[5]Henderson P.Rare Earth Element Geochemistry[M].Amsterdam:Elsevier Science Publishers,1984,1-510
[6]闫国强,丁俊,黄勇,等.西藏努日铜钼钨矿床辉钼矿微量元素、稀土元素地球化学特征——对矿床成矿流体性质的约束[J].矿物岩石地球化学通报,2015,34(3):564-570.
[7]刘晓文,李泽琴,王奖臻,等.扬子西南缘拉拉IOCG矿床辉钼矿微量元素地球化学特征[J].矿物岩石地球化学通报,2017,36(6):1 056-1 062.
[8]刘英俊,曹励明,李兆麟,等.元素地球化学[M].北京:科学出版社,1984.
[9]李逸群,颜晓锤.中国南岭及邻区钨矿床矿物学[D].武汉:中国地质大学出版社,1991:1-455.
[10]Shannon R D.Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides[J].Acta Crystallographica,1976,32(5):751-767.
[11]黎彤,袁怀雨.中国大陆壳体的区域元素丰度[J].地球化学,2011,40(1):1-5.
[12]黄凡,王登红,陈毓川,等.中国钼矿中辉钼矿的稀土元素地球化学及其运用[J].中国地质,2013,40(1):286-300.
[13]Taylor S R,McLennan S M.The continental crust:its composition and evolution[M].London:Blackwell,1985,57-72.
[14]Keppler H.Constraints from partitioning experiments on the composition of subduction zone fluids[J].Nature,1996,15(6):1 6320-1 6330.
[15]黄凡,王登红,曾载淋,等.赣南园岭寨大型钼矿岩石地球化学、成岩成矿年代学及其地质意义[J].大地构造与成矿学,2012,36(3):363-376.
[16]郑大中,郑若锋.稀土元素的迁移形式富集机理初探[J].化工矿产地质,2003,25(4):219-228.
[17]丁振举,刘丛强,姚书振,等.东沟坝多金属矿床矿质来源的稀土元素地球化学限制[J].吉林大学学报(地球科学版),2003,33(4):437-442.
[18]李光来.赣南及邻区燕山期花岗岩演化与钨成矿作用[D].南京:南京大学,2011.
[19]王登红,李超,陈郑辉,等.辉钼矿在矿床学研究中的新用途(I):稀土元素示踪[J].吉林大学学报(地球科学版),2012,42(6):1 647-1 655.
[20]Mao J W,Zhang X Y,Zhang Z C,et al.Temporo-Spatial Distribution and Evolution of Ore Deposits in the West Sector of the Northern Qilian Mountains[J].Acta Geologica Sinica(English Edition),1999,73(2):230-241
[21]黄典豪,吴澄宇,杜安道,等.东秦岭地区钼矿床的铼-锇同位素年龄及其意义[J].矿床地质,1994,13(3):221-230.
[22]李红艳,毛景文,孙亚利,等.柿竹园钨多金属矿床的Re-Os同位素等时线年龄研究[J].地质论评,1994,42(3):261-267.
[23]赵海香,戴宝章,李斌,等.小秦岭车仓峪钼矿成因研究:辉钼矿Re-Os年龄及黄铁矿微量元素制约[J].岩石学报,2015,31(3):784-790.
[24]倪智勇,李诺,张辉,等.河南大湖金钼矿床成矿物质来源的锶钕铅同位素约束[J].岩石学报,2009,25(11):2 823-2 832.
[25]Roser B P,Korsch R J.Provenance signatures of sandstone-mudstone suits determined using discriminant function analysis of major-element data[J].Chemical Geology,1988,67(1):119-139.
[26]李顺庭,王京彬,祝新友,等.湖南瑶岗仙钨多金属矿床辉钼矿Re-Os同位素定年和硫同位素分析及其地质意义[J].现代地质,2011,25(2):228-235.
[27]李闫华,鄢云飞,谭俊,等.稀土元素在矿床学研究中的应用[J].地质找矿论丛,2007,22(4):294-298.
[28]Florian K,Carsten M,Jonas T,et al.Accurate stable tungsten isotope measurements of natural samples using a180 W-183 W double-spike Original Research[J].Chemical Geology,2018,476:407-417.
[29]周云飞,徐九华,单立华,等.新疆巴里坤小加山钨矿地质特征与成因[J].地质通报,2016,35(12):2 121-2 132.
[30]Deng X H,Chen Y J,Santoshd M,et al.U-Pb zircon,Re-Os molybdenite geochronology and Rb-Sr geochemistry from the Xiaobaishitou W(Mo)deposit:Implications for Triassic tectonic setting in eastern Tianshan,NW China[J].Ore Geology Reviews,2017,80:332-351.
[31]Pan X F,Hou Z Q,Li Y,et al.Dating the giant Zhuxi W-Cu deposit(Taqian-Fuchun Ore Belt)in South China using molybdenite Re-Os and muscovite Ar-Ar system[J].Ore Geology Reviews,2017,86:719-733.