2. 中国科学院大学, 北京 100049
2. University of Chinese Academy of Sciences, Beijing 100049, China
右江盆地是我国卡林型金矿主要集中分布区之一,产有水银洞、烂泥沟、紫木凼、戈塘、泥堡、丫他、金牙、高龙等超大、大-中型卡林型金矿床。矿床以台地相不纯碳酸盐岩和盆地相细碎屑岩为主要容矿岩石,矿体明显受断裂控制,与As、Sb、Hg(Tl)等元素密切共生,具有去碳酸盐化、粘土化、硫化物化和硅化等围岩蚀变特征,类似于美国内华达州的卡林型金矿床(Hu et al., 2002; Su et al., 2009a)。二十多年来,前人已对该类金矿形成的地质背景与成矿条件、含金硫化物矿物学与地球化学、成矿流体特征与成矿年代、成矿机制与成矿模式等方面都进行了较多的研究(胡瑞忠等, 1995, 2007, 2015;朱赖民等, 1997, 1998a, b; 朱赖民和胡瑞忠, 1999;蒋国豪等,2000;Zhu and Hu, 2000; 贾大成和胡瑞忠,2001;Hu et al., 2002; 苏文超,2002;Wang et al., 2003; Zhang et al., 2003;陈懋弘等, 2006, 2007, 2009;张弘弢,2007;刘建中等,2008;Su et al., 2008, 2009a, b, 2012;夏勇等,2009;陈本金等,2010;罗刚,2010;Hu and Zhou, 2012; 张长青等,2012;代鸿章,2012;章永梅等,2013;Chen et al., 2015a, b; Tan et al., 2015;Hou et al., 2016)。
近年来的勘探实践,在右江盆地南缘发现一些金矿产于二叠纪辉绿岩体内部或辉绿岩与沉积岩接触带之中,如桂西北龙川、八渡以及滇东南安那等金矿床。这些金矿床在控矿构造、元素与矿物组合、热液蚀变以及金的赋存状态等方面,类似于盆地内以沉积岩为容矿岩石的卡林型金矿床,而在矿石品位、流体性质、成矿物质来源等方面与之存在差别(肖龙,1997;潘家永等,1998;覃文明和何志美,2003;陈新敏等,2011;寸伟才等,2011;覃少耀和颜小东,2012;Li et al., 2012;董文斗等,2013),前人对该类型金矿成矿流体性质与来源及其成矿过程等缺少系统的研究。本文通过对滇东南安那金矿床矿石显微岩相学结构、矿物学与地球化学、流体包裹体岩相学与显微测温学、激光Raman光谱以及氢氧同位素地球化学等分析,获取该类型金矿成矿流体性质和组成,探讨成矿流体的来源、演化及其成矿过程,对深入了解西南大面积低温成矿域的形成具有重要的科学意义。
1 区域地质背景与矿床地质特征安那金矿区位于右江盆地南缘的滇东南褶皱带文山-富宁断褶带东端(图 1),紧邻越北逆冲推覆褶皱带(Tran et al., 2016)。矿区主要出露泥盆系地层,主要为中下泥盆统灰黑色-灰绿色页岩、粉砂质泥岩和薄层泥灰岩夹黑色燧石条带,是矿区西南部革挡金矿床的赋矿层位。寒武系和奥陶系地层主要分布在矿区的西北部,主要为中-上寒武统灰黑色中厚层条带状白云岩和白云质灰岩,局部夹泥质粉砂岩、砂岩及透镜状燧石条带和中-下奥陶统灰白色中厚层石英砂岩、灰岩、白云岩和泥质灰岩,夹泥质粉砂岩和生物碎屑灰岩。石炭系地层零星分布,主要为浅灰色厚层状灰岩、生物碎屑灰岩和白云岩。二叠系和三叠系地层主要分布在矿区的东部,主要为灰岩、泥质粉砂岩、砂岩等。
矿区褶皱和断裂构造十分发育,自北向南主要有东西向南劳背斜、洞波向斜和者桑背斜等褶皱构造。断裂构造主要发育北东向叭洞和龙叭断裂以及东西向岩河和者桑南断裂,其次为北西向富宁弧形断裂。矿区内岩浆活动较为强烈,主要为二叠纪偏碱性辉长辉绿岩和苏长-辉长岩(Zhou et al., 2006),其主体侵位于泥盆系地层之中,围岩广泛发育角岩化等热接触交代蚀变,并伴随有铜矿化等。
安那金矿床产于东西向安那背斜的东部倾伏段(图 2)。背斜的核部为辉绿岩侵入,两翼地层为中泥盆统坡折落组硅质岩。目前发现V1、V2和V3三个矿体群(寸伟才等,2011),其中V1和V2矿体群呈似层状,产于背斜核部或两翼的辉绿岩与硅质岩接触部位的蚀变辉绿岩内。矿体一般长280~450m,厚0.63~23.6m,Au平均品位1.04×10-6~1.27×10-6。V3矿体群均产于蚀变辉绿岩内,矿体主要由石英脉和蚀变辉绿岩组成,受北东向张性裂隙控制,呈“雁行”式脉状产出,矿体长20~100m,厚0.5~2m,Au平均品位1.22×10-6。所有矿体均广泛发育乳白色石英脉或网脉(图 3a),金矿化强度与石英脉的发育程度及围岩蚀变程度有关,含金硫化物主要分布在石英脉两侧的蚀变辉绿岩中,石英脉中很少见有硫化物。以石英脉为中心,两侧的辉绿岩通常发育褪色蚀变带,远离石英脉,热液蚀变逐渐减弱。褪色蚀变主要为硅化、伊利石化、绢云母化、绿泥石化以及碳酸盐岩化等,金主要以不可见金的形式赋存在含砷黄铁矿和毒砂之中(图 3)。矿石中矿石矿物主要有黄铁矿、毒砂等,脉石矿物主要有石英、金红石、方解石、白云石、云母、伊利石、重晶石、绿泥石等。矿石构造主要为块状构造、浸染状构造。
本次研究样品主要采自安那金矿床露天开采的V2矿体(图 2、图 3a)。矿石主要由石英脉和蚀变辉绿岩组成(图 3b)。金矿化主要发育在蚀变辉绿岩内,并伴随黄铁矿化、毒砂化等矿化,硅化、伊利石化、绢云母化、绿泥石化以及碳酸盐岩化等褪色热液蚀变,而石英脉中很少见有黄铁矿和毒砂等硫化物。载金矿物主要为黄铁矿和毒砂(图 3d),金主要以不可见金的形式存在。电子探针波谱成分分析显示,黄铁矿含有As(0.56%~4.22%)和Au(300×10-6~1010×10-6),毒砂含有Au(300×10-6~1290×10-6)。
选取石英单晶体沿C轴切割,磨制双面抛光的流体包裹体片(厚度约200μm)进行流体包裹体观察,然后选择有代表性的包裹体开展显微测温学和激光拉曼光谱分析。流体包裹体观察和显微测温学分析在中国科学院地球化学研究所矿床地球化学国家重点实验室完成,使用仪器为英国Linkam公司THMSG 600型冷热台和配有成像分析系统的标准显微镜。实验之前,采用国际人工合成流体包裹体标样对冷热台进行了校正。在低温(<50℃)和高温(>100℃)条件下,仪器误差分别为±0.1℃,±2℃。单个流体包裹体的气相成分分析采用英国Renishaw公司的InVia Reflex型显微共聚焦激光拉曼光谱仪,氩离子激光器波长为514nm,激光功率20mw,空间分辨率为1μm,扫描时间为30~60s,扫描范围为150~4000cm-1。石英氢氧同位素分析在中国地质科学院矿产资源研究所稳定同位素实验室MAT-253质谱仪上完成。氧同位素分析采用传统的BrF5分析方法(Clayton and Mayeda, 1963),即采用BrF5与石英(180目)在真空和高温条件下反应提取矿物中的氧,与电阻石墨棒燃烧转化成CO2气体用于质谱测定,氧同位素分析精度为±0.2‰。氢同位素分析则先将挑纯的石英(40~60目)在150℃下真空去气4h以上,以消除表面吸附水和次生包裹体水,然后在400℃高温下爆裂提取水,并与金属锌反应生成H2用于质谱测定,氢同位素分析精度为±2‰。
3 结果与讨论 3.1 流体包裹体岩相学对安那金矿床石英中200余个流体包裹体片进行了观察。根据流体包裹体在室温下的相态,结合降温过程中流体包裹体的相态变化和激光Raman光谱分析,发现石英中的流体包裹体均为CO2-H2O流体包裹体(图 4a)。这些流体包裹体呈负晶形,直径为5~90μm,气液比约为20%,通常沿石英的生长环带分布(图 4a),应为原生流体包裹体。室温下(25℃),该类流体包裹体通常为液态CO2(LCO2)和H2O两相(图 4a),降温时总是出现CO2气相,变为CO2-H2O三相流体包裹体(LH2O+LCO2+VCO2)。
利用冷热台对安那金矿床石英中120余个包裹体的盐度和均一温度进行了测定,其结果见表 1和图 5。
结果显示,在降温-冷冻过程中,该类流体包裹体总是出现气相CO2和固态CO2。所有包裹体CO2气相都均一到CO2液相,其均一温度(ThCO2)为10.8~28.2℃,平均15.3℃(图 4g、图 5c),计算的CO2密度为0.67~0.86 g/cm3,平均0.82 g/cm3;固态CO2的熔化温度(TmCO2)一般为-59.7~-56.8℃,平均-58.1℃,(图 4c、图 5d),低于纯CO2的三相点(-56.6℃),暗示可能含有CH4、N2等气体成分(Burruss, 1981;Shepherd et al., 1985)。激光Raman光谱分析进一步确认该类流体包裹体气相成分主要为CO2,含有少量的N2和微量的CH4(图 6)。在升温过程中,这些流体包裹体可以明显观察到CO2络合物的形成和熔化。CO2络合物的熔化温度(Tmclath)为9.0~10.3℃之间,平均为9.9℃,计算盐度为0~2.0% NaCleqv(Diamond, 1992),平均0.3% NaCleqv(图 4d、图 5b)。在加热过程中,部分流体包裹体在190~260℃之间发生了爆裂,未爆裂的流体包裹体均一到液相,其均一温度变化范围为208~312℃,主要集中在233~273℃之间,平均为254℃(表 1、图 5a),明显高于右江盆地以沉积岩为容矿岩石的卡林型金矿床(210℃)(Su et al., 2009a)。
对安那金矿床矿石中15条石英脉的氢氧同位素组成进行了分析,其结果见表 2和图 7。
可以看出,石英流体包裹体中H2O的δD值变化范围为-79‰~-47‰,与邻近者桑金矿床石英流体包裹体氢同位素变化范围(-75‰~-40‰)和滇东南中生代大气降水的氢同位素组成(-75.0‰)相近(代鸿章等,2014)。石英的δ18O值变化范围为18.6‰~22.4‰,根据Friedman and O’Neil(1977)石英-水氧同位素平衡分馏方程(δ18OQz-δ18OH2O=3.38×106/T2-2.9),计算获得H2O的δ18O值变化范围为8.9‰~12.7‰,明显高于昆明和贵州地区大气降水的氧同位素组成(图 7)。在δD-δ18O图解中,除1个样品点落入岩浆水范围内之外,其余所有样品点均落在变质水范围内或附近(图 7),表明安那金矿床成矿流体主要来源于变质流体,并与围岩发生了不同程度的水-岩交换反应。
以上研究表明,安那金矿床成矿流体为低盐度(0~2% NaCleqv)、中温(233~273℃)、富含CO2的变质流体,与造山型金矿成矿流体特征相似(Ridley and Diamond, 2000),有别于右江盆地以沉积岩为容矿岩石的卡林型金矿相对低温(210℃)、中等盐度(~6% NaCleqv)、低CO2含量的成矿流体特征(Su et al., 2009a)。对安那金矿床蚀变辉绿岩矿石中伊利石的40Ar-39Ar定年表明,该矿床形成于印支期(232±5Ma)(未发表),因此,认为这种变质流体可能与印支期右江盆地南缘越北逆冲推覆造山变质事件有关(Zaw et al., 2014; Tran et al., 2016)。
3.4 金的沉淀富集机制实验研究表明,在中低温( < 250℃)、富H2S的弱酸性热液条件下,Au主要以Au(HS)2-或Au(HS)0的形式迁移(Seward, 1973, 1993),而As则主要以H3AsO3的形式存在(Heinrich and Eadington, 1986;Pokrovski et al., 2002)。Au的沉淀富集一般认为与流体-岩石相互作用、流体混合以及流体不混溶过程等有关(Seward, 1973;Naden and Shepherd, 1989;Groves and Foster, 1991;Nesbitt,1991)。
流体包裹体研究表明,安那金矿床仅发育低盐度(0.3% NaCleqv)、中温(254℃)、富含CO2-H2O流体包裹体,缺乏沸腾流体包裹体组合。成矿流体氢氧同位素组成显示变质流体来源,暗示流体不混溶或流体混合可能不是该类型金矿床金沉淀富集的关键控制因素。热力学计算表明,在中低温( < 250℃)条件下,这种富含CO2的成矿流体具有弱酸性(pH=5.07~5.21)(Hofstra and Cline, 2000)。这种弱酸性的含Au热液可以使赋矿的辉绿岩中的含Ti-Fe辉石或者钛铁矿溶解释放Fe2+,为硫化物的形成和Au的沉淀富集提供了Fe的来源,溶解Fe的硫化作用过程使含Au黄铁矿和毒砂富集在金红石的边缘(图 3d),保留钛铁矿原始晶体形态,并伴随伊利石化、绿泥石化等热液蚀变,如钛铁矿与含Au热液的化学反应:
通过对滇东南安那金矿床流体包裹体岩相学、显微测温学以及氢氧同位素地球化学等研究,获得以下认识:
(1)安那金矿床成矿流体具有低盐度(0~2% NaCleqv)、中温(233~273℃)、富含CO2的流体特征,与造山型金矿成矿流体特征相似,其成矿动力学背景可能与右江盆地南缘印支期越北逆冲推覆造山事件有关。
(2)成矿流体氢氧同位素组成显示变质流体成因,结合矿石显微岩相学结构,认为变质流体溶蚀交代辉绿岩中的含Ti-Fe辉石或者钛铁矿,溶解Fe的硫化作用过程是含Au黄铁矿和毒砂沉淀富集的重要机制。
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