2022, Vol. 38
2. 中国地质大学地质过程与矿产资源国家重点实验室，北京 100083;
3. 盛屯矿业集团股份有限公司，厦门 361012
2. State Key Laboratory of Geological Processes and Mineral Resources, China University of Geosciences, Beijing 100083, China;
3. Shengtun Mining Group Co. Ltd, Xiamen 361012, China
峨眉山大火成岩省产出一大批成岩成矿一体的镁铁-超镁铁质岩体及黑色和稀有金属矿床(胡瑞忠等, 2005; Zhou et al., 2008)，如攀西(攀枝花-西昌)地区的钒钛磁铁矿床和铜镍硫化物及铂族元素矿床，前者钒、钛储量占到世界的一半左右(宋谢炎等, 2018)。此外，区带上产出众多同时代不成矿的镁铁-超镁铁质岩体，范围遍布扬子克拉通西缘的攀西到松潘-甘孜地区(王登红等, 2007)，其中在攀西地区研究相对较多(赵正等, 2012; 刘军平等, 2020)，在松潘-甘孜地区报道较少。上述不成矿岩体同为峨眉山玄武质岩浆结晶分异作用的产物(张招崇等, 2001; 徐义刚和钟孙霖, 2001; Xu et al., 2003, 2008)。显然，具有相似岩浆演化过程和紧密时空联系的(超)基性岩体成矿差异性是有关该区域黑色和稀有金属矿床找矿勘查的重要科学问题。
氧逸度通过控制岩浆熔体中的变价元素，尤其是铁的氧化还原态来改变矿物结晶顺序和成分(Lee and Tang, 2020)。高岩浆氧逸度可以促使Fe-Ti氧化物较早结晶，可能在攀枝花钒钛磁铁矿形成过程中发挥关键作用(Ganino et al., 2008; Bai et al., 2019)。罗雕等(2020)报道了攀枝花钒钛磁铁矿岩体苦橄岩和浅色辉长岩的锆石微量数据，认为其估算的较高氧逸度源自扬子克拉通西缘不均一的高氧化态地幔源区。此外，分离结晶作用对钒钛磁铁矿成矿有重要影响(宋谢炎等, 2005; 汤庆艳等, 2013)。Fe-Ti氧化物通常与橄榄石和辉石同时结晶(Howarth and Prevec, 2013; Bai et al., 2019)，因此高结晶分异程度往往伴随更彻底的Fe-Ti氧化物沉淀。综上所述，分离结晶作用和高氧逸度是钒钛磁铁矿形成的重要条件，但根据鲍文演化序列二者为相互促进关系(Charlier et al., 2015)，哪种因素起主导作用尚不明确。
扬子西缘丹巴地区散布暂无经济价值的(超)基性岩体，其中基性岩墙群时代多为新元古代(Lin et al., 2007)。本文选取尚无精确年龄限定的水子乡辉石岩为研究对象，其锆石U-Pb定年结果为~260Ma。该岩体与攀枝花地区~260Ma钒钛磁铁矿岩体同为扬子克拉通西缘峨眉山大火成岩省的产物，均发育粗晶辉石岩-粗晶辉长岩-细粒辉长岩相变(胡世华等, 2000①; Zhang et al., 2009; Bai et al., 2012)，可分别作为不成矿和成矿岩体代表。本文运用锆石微量元素估算二者岩浆氧逸度，并探讨二者结晶分异程度与成矿关系。
① 胡世华, 李云泉, 曾宜君, 杨学俊, 刘开榜, 刘建清, 李开元. 2000. 1/5万丹巴幅区域地质调查报告. 四川省地质矿产勘查开发局
1 地质背景 1.1 峨眉山大火成岩省峨眉山大火成岩省位于扬子克拉通西缘(图 1a)，主要由大规模的大陆溢流玄武岩和少量(超)基性岩侵入体以及同源的正长岩、花岗岩组成(Shellnutt and Zhou, 2007; Zhong et al., 2007)。溢流玄武岩是峨眉山大火成岩省喷出岩的主体，可分为高钛和低钛系列(张招崇等, 2001; 徐义刚等, 2007)。(超)基性岩侵入体主要分布在大火成岩省南部攀西地区(图 1a)，除超大型攀枝花钒钛磁铁矿岩体群外，也零星分布中、小型成矿岩体(叶小春等, 2019)，其余多为不成矿岩体(刘军平等, 2020)。(超)基性岩侵入体在大火成岩省北端松潘-甘孜地区分布较少(图 1a)，除形成大型杨柳坪铜镍硫化物及铂族元素矿床的岩体外，丹巴水子乡辉石岩体为规模较大的不成矿岩体(胡世华等, 2000)。正长岩和花岗岩主要分布在攀枝花钒钛磁铁矿岩体群范围内(钟宏等, 2008)。
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图 1 丹巴水子乡辉石岩地质背景及区域地质图 (a)峨眉山大火成岩省地质图(据Xu et al., 2007, 除本文外的成岩成矿年龄据Zhang et al., 2009及其中文献)；ANHF-安宁河断裂；MPSF-磨盘山断裂；PZHF-攀枝花断裂；XSHF-鲜水河断裂；(b)丹巴水子乡辉石岩地质图(据胡世华等, 2000) Fig. 1 Geological background and regional geological map of the Shuizi pyroxenite at Danba (a) geological map of the Emeishan Large Igneous Province (modified after Xu et al., 2007). The ages from Zhang et al. (2009) and references therein. ANHF-Anninghe Fault; MPSF-Mopanshan Fault; PZHF-Panzhihua Fault; XSHF-Xianshuihe Fault. (b) geological map of the Danba area containing the Shuizi pyroxenite |
扬子克拉通西缘出现新元古代岛弧特征的侵入岩-变质岩组合，被认为与860~750Ma期间大洋岩石圈俯冲到扬子板块之下有关(Zhou et al., 2002; Zhao and Zhou, 2008)。这套弧岩浆组合及其变质形成的花岗质片麻岩、混合岩以及残留的元古代沉积变质岩构成了扬子西缘基底的主体(图 1a)。基底之上为不整合覆盖的古生代地层(Roger et al., 2010)，其中二叠系地层岩石主要为碳酸盐岩和峨眉山玄武岩。古生代地层之上不整合覆盖以三叠系复理石建造为主的中、新生代地层(Yan et al., 2003)。
扬子克拉通西缘沿龙门山-锦屏山逆冲推覆带发育>1000km的晚古生代-中生代穹窿带(He et al., 2003; Zhao et al., 2019)。南部攀西地区的南北向岩石圈规模断裂控制(超)基性岩体产出，如攀枝花岩体群的产出范围限定在安宁河断裂、磨盘山断裂和攀枝花断裂之间(图 1a)；北端松潘-甘孜地区(超)基性岩体产出于鲜水河断裂的次级断裂带(图 1a)。
攀枝花岩体群为成矿的镁铁质-超镁铁质层状岩体(邓军等, 2014; Bai et al., 2019)，如攀枝花、红格、新街、白马和太和等岩体赋存钒钛磁铁矿矿床；力马河等岩体赋存铜镍硫化物及铂族元素矿床(图 1a)。不管赋存何种类型矿床，这些岩体的成岩成矿年龄均集中在~260Ma(Zhang et al., 2009)。其中攀枝花、白马和太和岩体为辉长岩相控矿，红格和新街岩体为辉石岩相控矿(Bai et al., 2012; Hou et al., 2013)。
1.2 攀枝花钒钛磁铁矿岩体攀枝花层状岩体侵位于新元古代灯影组白云质灰岩/大理岩中，赋存的钒钛磁铁矿床矿石储量为1.333Mt，平均品位为TFe=33%、TiO2=12%、V2O5=0.3%(马玉孝等, 2003)。攀枝花岩体自下而上分为：含辉石橄榄石边缘相带、含大量钒钛磁铁矿矿层的辉长岩相带、含少量钒钛磁铁矿矿层的辉长岩相带、浅色辉长岩相带(Zhang et al., 2009)。苦橄岩产出于边缘相带，其全岩Ti含量为0.7×10-6~1.4×10-6，锆石U-Pb年龄为261.4±4.6Ma(Hou et al., 2013)。浅色辉长岩含大量粗粒斜长石，锆石U-Pb年龄为259.8±0.8Ma(Hou et al., 2012)。岩体上部出露晚期分异形成的斜长岩(Hou et al., 2012)。此外，攀枝花地区二滩和龙帚山玄武岩全岩Ti含量分别为~2.8×10-6和~3.5×10-6(Bai et al., 2014)。
2 水子乡辉石岩岩体水子乡辉石岩岩体位于丹巴县城南西(图 1b)，侵位于志留系通化组角闪岩相变质地层，围岩为二云石英片岩和石英岩等(图 2a)。岩体有弱的相变分带，由巨晶辉石岩-粗晶辉石辉长岩-中粒辉长岩组成，其主体为粗晶辉石岩(胡世华等, 2000)。粗晶辉石岩为深灰色到墨绿色(图 2b)，略具堆晶特征(图 2c)，主要矿物为单斜辉石(普通辉石)，受风化蚀变影响，其部分晶体边缘或全部转变为角闪石和黑云母(图 2d)。水子乡辉石岩体南南西约15km为杨柳坪超基性岩体，产出铜镍硫化物铂族元素矿床(王登红等, 2007)；岩体以东区域上的二叠系大石包(变)玄武岩全岩Ti含量为1.4×10-6~3.2×10-6(平均2.2×10-6；胡世华等, 2000)。
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图 2 丹巴水子乡辉石岩野外及镜下照片 (a)辉石岩侵入志留系变质岩；(b)辉石岩手标本照片；(c)略具堆晶特征的粗粒辉石岩；(d)辉石多蚀变为角闪石及黑云母 Fig. 2 Field, hand specimen and microscopic photos of the Shuizi pyroxenite in the Danba area (a) the pyroxenite emplaced into the high-grade metamorphic Silurian rocks; (b) hand specimen photograph of the pyroxenite; (c) the coarse-grained pyroxenite with mild cumulate structures; (d) clinopyroxene (Cpx) replaced by amphibole (Amp) and biotite (Bt) |
本次研究使用的单颗粒锆石样品挑选自丹巴水子乡粗晶单斜辉石岩(图 2b)，其与对比对象攀枝花岩体苦橄岩和浅色辉长岩的特征见表 1。锆石LA-ICP-MS U-Pb定年及微量元素分析在北京中国地质科学院地质研究所完成，使用的仪器为Agilent 7900 ICP-MS及配套的NWR 193UC激光剥蚀系统，束斑直径为25μm，剥蚀速率为5Hz，激光能量为2J/cm2。锆石91500和NIST610作为标样，锆石GJ-1和Plešovice用于数据质量评估。数据处理使用Iolite软件(Paton et al., 2010)，206Pb/238U加权平均年龄计算使用Isoplot 3.0(Ludwig, 2003)。
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表 1 丹巴水子乡辉石岩与攀枝花岩体(超)基性岩特征对比表 Table 1 Characteristics of the Shuizi pyroxenite in the Danba area and mafic-ultramafic rocks from the Panzhihua intrusion |
水子乡辉石岩锆石U-Pb定年结果见表 2。206Pb/238U加权平均年龄为260.7±3.3Ma(MSWD=0.16，N=20；图 3a)。水子乡辉石岩锆石微量元素测试结果见表 3，其稀土元素含量在1000×10-6~4000×10-6之间，稀土元素配分形式与攀枝花苦橄岩和浅色辉长岩锆石大体一致(图 4a)。相比之下，水子乡辉石岩锆石轻稀土含量稍高，重稀土部分更为平坦，Eu负异常更不明显(图 4a)；攀枝花苦橄岩和浅色辉长岩锆石Ti、Nb和Ta含量明显偏低(图 4b)。水子乡辉石岩锆石Hf含量为4200×10-6~9700×10-6，比攀枝花苦橄岩和浅色辉长岩锆石6800×10-6~11500×10-6低(图 5、图 6)。水子乡辉石岩锆石微量元素估算的代表岩浆氧逸度的ΔQFM值(logfO2(sample)-logfO2(FMQ)，样品氧逸度相对于铁橄榄石-磁铁矿-石英缓冲剂的值；Loucks et al., 2020)主要在0~3.1范围内(平均~1.0；图 5a, b)，Ce异常(CeN/CeN*=CeN·SmN/NdN2；Loader et al., 2017)为4~125(平均30；图 5c, d)。
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表 2 丹巴水子乡辉石岩锆石LA-ICP-MS U-Pb数据 Table 2 Zircon LA-ICP-MS U-Pb data of the Shuizi pyroxenite in the Danba area |
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图 3 丹巴水子乡辉石岩锆石LA-ICP-MS U-Pb协和图(a)及阴极发光照片(b) Fig. 3 Zircon LA-ICP-MS U-Pb concordia diagram (a) and cathodoluminesence (CL) images (b) of the Shuizi pyroxenite in the Danba area |
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表 3 丹巴水子乡辉石岩锆石微量元素含量(×10-6)、Th/U比值及氧逸度估算值 Table 3 Trace elements (×10-6), Th/U ratios, and estimated oxygen fugacity values of zircon from the Shuizi pyroxenite in the Danba area |
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图 4 丹巴水子乡辉石岩及攀枝花岩体锆石球粒陨石标准化稀土元素配分形式(a, 标准化值据Sun and McDonough, 1989)和原始地幔值标准化微量元素蛛网图(b, 标准化值据McDonough and Sun, 1995) Fig. 4 Chondrite-normalized REE patterns (a, normalization values after Sun and McDonough, 1989) and primitive mantle-normalized trace element diagram (b, normalization values after McDonough and Sun, 1995) for zircons from the Shuizi pyroxenite in the Danba area and those from the Panzhihua intrusion |
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图 5 丹巴水子乡辉石岩及攀枝花岩体锆石微量元素估算岩浆氧逸度及其与锆石Hf含量关系图 Fig. 5 Estimation of the oxygen fugacity of the Shuizi pyroxenite in the Danba area and those from the Panzhihua intrusion based on zircon trace element contents and their evolution trends relative to Hf contents |
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图 6 丹巴水子乡辉石岩及攀枝花岩体分离结晶程度差异 Fig. 6 Difference of fractional crystallization degrees for the Shuizi pyroxenite in the Danba area and those for the Panzhihua intrusion |
尽管丹巴水子乡辉石岩体早已发现，但尚无年龄报道(胡世华等, 2000)。本次锆石LA-ICP-MS U-Pb测年结果为260.7±3.3Ma(图 3a)。锆石应用于超基性岩研究相对较少，主要原因是(超)基性岩大多数情况下硅、锆不饱和，因而锆石较为稀少(吴元保和郑永飞, 2004)。此外，超基性岩中挑选出的锆石是否为原生岩浆锆石存疑(宫江华等, 2020)。这类岩石事实上很难挑选出锆石用于测年，其锆石在形成过程、野外采样和挑选单矿物过程中容易混入其它来源锆石，造成混乱的年龄结果(宫江华等, 2020)。然而镁铁质岩浆经历一定程度演化，结晶出来的岩相仍是(超)基性岩(如本文略具堆晶特征的单斜辉石岩；图 2c)，但是硅、锆可以饱和并生成锆石(Xue et al., 2016, 2019; Wang et al., 2018, 2020b, 2021)。攀西地区近年也有较高精度镁铁-超镁铁质岩锆石U-Pb年龄报道(叶小春等, 2019; 刘军平等, 2020；代堰锫等，2021)。
丹巴辉石岩锆石Th/U比为0.4~4.5(表 2)，不发育环带或环带很宽(图 3b)，为典型的(超)基性岩浆锆石，反映微量元素在高温条件下的快速扩散(吴元保和郑永飞, 2004)。部分锆石边缘发育少量浅色的变质增生边(图 3b)。然而所有锆石核部测得年龄非常均一，在误差范围内一致(图 3a)，测得的微量元素也相对均一(图 4)，]表明所测锆石核部U-Pb同位素体系和微量元素未明显受到后期变质影响(Liu et al., 2010)。总的来说，丹巴辉石岩锆石为原生岩浆锆石，261±3Ma的年龄表明其为~260Ma峨眉山大火成岩省北端松潘-甘孜岩区镁铁-超镁铁质岩的组成部分(王登红等, 2007)。
5.2 水子乡辉石岩高氧逸度本文采用锆石ΔQFM、CeN/CeN*和EuN/EuN*三种方法估算水子乡辉石岩和攀枝花岩体岩浆氧逸度。为验证方法可靠性，引用攀枝花岩体锆石前人数据并采用相同方法计算所得ΔQFM在0~3，平均~1.5，与前人结果一致(表 3; 罗雕等, 2020)。该结果与同样针对攀枝花岩体但采用橄榄石-尖晶石矿物对估算方法所得ΔQFM范围也一致(Bai et al., 2019)。以上表明锆石ΔQFM值为反映岩浆氧逸度的可靠指标(Loucks et al., 2020; 邹心宇等, 2021)。运用锆石ΔQFM估算得出水子乡辉石岩氧逸度为0~3.1，平均~1.0，与攀枝花岩体值相当(图 5a, b)。采用锆石CeN/CeN*估算所得水子乡辉石岩与攀枝花岩体氧逸度也基本一致(图 5a, c)，表明锆石CeN/CeN*也是反映此两处岩体岩浆氧逸度的可靠指标(Loader et al., 2017)。相比之下，运用锆石EuN/EuN*估算的攀枝花岩体氧逸度比水子乡辉石岩明显偏低(图 5c)，可能是因为前者斜长石分离结晶导致残余岩浆显著Eu负异常(Snyder et al., 1993)。因此运用锆石Eu异常反映攀枝花岩体岩浆氧逸度并不可靠。
锆石ΔQFM和CeN/CeN*估算表明水子乡单斜辉石岩与攀枝花苦橄岩和浅色辉长岩具有相近的较高氧逸度(图 5)。较高氧逸度的特征是源于岩浆演化还是母岩浆本身仍有一定争议(罗雕等, 2020)。本文岩浆氧逸度与反映岩浆分离结晶程度的锆石Hf含量呈一定正相关关系(图 5b, d)，暗示随岩浆结晶分异进行，氧逸度有略微升高，可能是温度降低和/或成分变化等造成(Liu et al., 2010)。橄榄石和辉石分离结晶会消耗岩浆体系中的Fe2+，导致残余熔体氧逸度小幅升高(Ghiorso, 1997)，但在此二者分离结晶对氧逸度的影响非常有限(图 5b, d)。攀枝花岩体侵位过程中，其围岩大理岩被同化导致CO2的加入可能引起氧逸度升高(Zhou et al., 2005; Pang et al., 2008)。然而Re-Os、Sr-Nd和O同位素等分析表明攀枝花岩体未受到明显地壳混染(Hou et al., 2013; Yu et al., 2015)。水子乡辉石岩体围岩并非碳酸盐岩(图 2a)，也显示出较高氧逸度，从侧面印证围岩混染对氧逸度的影响微弱。因此，水子乡辉石岩和攀枝花岩体较高氧逸度的特征应源于母岩浆本身，且均可能继承自峨眉山大火成岩省的较高氧逸度、不均一地幔源区(Hou et al., 2011; Bai et al., 2019)。扬子克拉通西缘的岩石圈地幔在新元古代受到洋壳板片俯冲交代(Zhou et al., 2002; Hou et al., 2011; Wang et al., 2020a)。此类俯冲作用在峨眉山大火成岩省和中国东部板内玄武岩均有地球化学记录(Deng et al., 2017; Ren et al., 2017; Xu et al., 2018)。俯冲板片释放H2O-CO2流体使得交代岩石圈地幔氧逸度升高(Foley, 2011; Gerrits et al., 2019)，可到ΔQFM~2(Malaspina and Tumiati, 2012)。
5.3 高氧逸度与钒钛磁铁矿成矿前人研究表明镁铁-超镁铁质岩浆在高氧逸度环境下，Fe-Ti氧化物(磁铁矿-钛铁尖晶石、钛铁矿-赤铁矿固溶体)较早饱和沉淀(Toplis and Carroll, 1995; Jugo, 2009; Jugo et al., 2010)。较高氧逸度使得水子乡辉石岩具备成矿条件之一，暗示含钛磁铁矿可能在其深部岩浆房已经饱和卸载。然而水子乡辉石岩锆石高Ti含量(图 6a)及其对应的全岩Ti含量，明显高于区域上玄武岩全岩Ti含量(1.4×10-6~3.2×10-6；胡世华等, 2000)，暗示水子乡辉石岩岩浆演化过程中并未明显抽提过Ti，即大量Fe-Ti氧化物的分离结晶，在此氧逸度可能是次要影响因素。由于镁铁-超镁铁质岩浆演化过程中Fe-Ti氧化物基本与硅酸盐矿物同时结晶(Howarth and Prevec, 2013; Bai et al., 2019)，而水子乡辉石岩只发育弱的岩相分带(胡世华等, 2000)，其较低的结晶分异程度不利于含钛磁铁矿沉淀，在此可能是主要影响因素。前人研究认为岩浆高度演化/高结晶分异造就共结硅酸盐矿物被移出而Fe-Ti氧化物遗留岩浆房对攀枝花钒钛磁铁矿矿床形成至关重要(Bai et al., 2019)。
攀枝花苦橄岩和浅色辉长岩锆石Ti不饱和，并随岩浆结晶分异程度增加进一步亏损(图 6a)，其低Ti含量对应全岩低Ti含量(0.75×10-6~1.39×10-6；Hou et al., 2012)，后者远低于区域上玄武岩全岩Ti含量(2.8×10-6~3.5×10-6；Bai et al., 2014)，表明攀枝花岩体经历过Ti的抽提，即Fe-Ti氧化物的分离结晶(Hou et al., 2011)，与大规模钒钛磁铁矿成矿现象一致。Nb、Ta对于暗色矿物辉石是不相容元素，且一般进入金红石等Ti-Fe氧化物(Stepanova et al., 2014)，因此Nb、Ta在水子乡岩体辉石分离结晶过程中富集到残留熔体，但在攀枝花岩体钛磁铁矿分离结晶过程中亏损(图 6b)。上文已述及，随斜长石分离结晶进行，残余岩浆Eu负异常加剧(图 6c)，这与攀枝花浅色辉长岩含大量粗粒斜长石、岩体上部有晚期结晶分异产物斜长岩以及矿区有同源正长岩和花岗岩的地质现象一致(Shellnutt and Zhou, 2007; 钟宏等, 2008)。总的来说，攀枝花岩体经历了比水子乡辉石岩体更高程度的Fe-Ti氧化物和斜长石的分离结晶作用(图 5、图 6)，这是除高氧逸度外钒钛磁铁矿矿床形成的关键条件之一(宋谢炎等, 2005; 汤庆艳等, 2013)。
6 结论(1) 扬子西缘丹巴地区水子乡~260Ma辉石岩为峨眉山大火成岩省北端松潘-甘孜岩区镁铁-超镁铁质岩的组成部分。
(2) 水子乡单斜辉石岩具有与攀枝花钒钛磁铁矿岩体苦橄岩和浅色辉长岩近似的高岩浆氧逸度，较高氧逸度是钒钛磁铁矿成矿的重要条件。
(3) 水子乡辉石岩岩体经历了相对低程度的结晶分异，不利于钛磁铁矿饱和结晶；攀枝花岩体经历了更高程度的钛磁铁矿和斜长石分离结晶，对应大规模钒钛磁铁矿成矿。
致谢 两位审稿专家对论文提出了许多宝贵的建设性意见和建议，在此致以衷心感谢。感谢中国地质大学(北京)张静老师和《岩石学报》编辑部俞良军老师等对论文提出的修改意见和建议。
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