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2017年以来，包括铟在内的稀散金属（主要有铟、镓、锗、铊、硒、碲、铼、锶、钡）的安全供应上升至国家发展战略高度，全球范围内又掀起了新一轮的研究热潮。虽然铟被列为用量不大的“小宗”矿产，但是添加极少的量即可以极大地提升物质特性，使得铟在许多重要高新技术领域的不可替代地位日益凸显，如太阳能电池中的铜铟镓硒（CIGS）、显示器中的铟锡氧化物（ITO）、电脑芯片、半导体、焊料及合金（蒋少涌等，2020；王学求等，2021；周艳晶，2021），其中ITO（indium tin oxides）靶材占全球铟消费量的70%（周艳晶，2021）。铟主要以类质同象方式赋存于闪锌矿中（张乾等，2003；伍永田，2009），约95%的铟产量来自于闪锌矿；全球对铟的需求每年增长约15%，而锌产量年增长率预计仅为1%~3%，因此铟供应难以满足中长期的需求（Gómez et al.，2023）。
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牟保磊（1999）估算铟在地壳中的平均含量仅为0.14×10-6，其在不同的地质环境下可表现出亲硫、亲石元素的特征（李晓峰等，2020）。超低的地壳丰度致使铟在绝大多数情况下难以形成独立矿床，仅以伴生组分形式赋存在各类“大宗”矿产中。目前全世界已探明的铟储量约79000 t（李晓峰等，2020），大部分集中在中国、玻利维亚、俄罗斯、加拿大、日本和德国，上述国家占全球铟储量的84%，中国位居世界第一（约占26%；李芳琴等，2022）。目前来看，桂西南—滇东南地区大厂、都龙、个旧和老厂锡石-硫化物矿床中铟品位极高，是目前我国含铟矿石最重要的来源（李晓峰等，2020）。
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基于中国地质调查局地质大调查项目“国内外三稀信息集成”和“矿产资源国情调查数据集成与动态更新”的数据库资料，中国目前有57个伴生铟矿床（图1）。本文整理了20世纪80年代以来文献报道的上述矿床已有的成岩成矿年龄、全岩地球化学、含铟矿物的元素含量等数据。基于以上研究，归纳总结了我国伴生铟矿床的成因类型、区域分布、形成时代、独立铟矿物、赋存矿物、富集规律等特征，并进一步讨论了我国铟资源研究和探查的未来方向。
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1 中国伴生铟矿床类型
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目前，国内外对伴生铟矿床类型有多种划分方案。张乾等（2003）将富铟矿床归类为两类：以海底喷流沉积为主但受到中酸性岩浆影响的矿床和以岩浆作用为主的矿床。Schwarz-Schampera et al.（2002）将含铟矿床划分为8类：矽卡岩型、脉状钨锡矿型、块状硫化物型（VMS）、斑岩型、喷流沉积型（SEDEX）、浅成低温热液型、多金属脉型和与岩浆作用有关的类型。Ishihara et al.（2006）认为铟主要来源于两大类矿床：一类是块状硫化物矿床，另一类是浸染状、脉状与矽卡岩矿床。赵汀等（2019）将我国的铟矿床归纳为6个主要的类型：热液型、矽卡岩型、陆相火山岩型、砂锡型、硫化物型和硫酸盐型。
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本文依据中国地质调查局“中国矿产地质志”项目建立的标准（表1），将伴生铟矿床统一划归至“三级分类”。我国57个伴生铟矿床可以归类为：矽卡岩型矿床28个，岩浆-热液型矿床14个，海相火山岩型矿床6个，叠加（复合/改造）型矿床5个，陆相火山岩型矿床2个，斑岩型矿床1个，受变质型矿床1个（附表1）。总体来看，我国伴生铟矿床中，与岩浆作用有关的矿床数量占绝对优势，为总数的89.5%，叠加（复合/改造）矿床占8.8%，变质作用矿床占1.7%。铟在矿石中的含量差异巨大，其中矽卡岩型矿床矿石中的铟含量峰值可达3940×10-6（湖南七宝山矿床），海相火山岩型矿床的矿石中铟含量可低至0.5×10-6（甘肃白银厂矿床小铁山矿段）。
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（1）矽卡岩型（28个）。中国伴生铟矿床最主要类型为矽卡岩型，占所有矿床总数的49.1%，矿床规模一般可达到中型以上，此类矿床主要分布在中亚造山带和华南地区（包括华夏地块和扬子地台；图2）。典型矿床为位于扬子地台西南缘的大厂、都龙、个旧。以储量最高的大厂矿床为例，该矿床出露于丹池成矿带中部，赋存于泥盆系和石炭系地层中（李晓峰等，2010；戴塔根等，2012；皮桥辉，2015），形成时代为早白垩世晚期—晚白垩世早期（梁婷，2008），郭佳（2019）认为其形成与新特提斯板块后撤导致幔源岩浆底侵有关。目前大厂矿床已探明矿石储量80 Mt，70%产于长坡-铜坑矿体，其中锡资源量0.56 Mt，铜资源量1.12 Mt，铅资源量2.8 Mt，锌资源量1.76 Mt，还伴生有Sb、Ga、Ag、In（8000 t）（Ishihara et al.，2011；徐净等，2018；郭佳，2019）。矿体形态呈似层状和脉状，矿石矿物以锡石-硫化物为主（锡石、铁闪锌矿、黄铁矿、磁黄铁矿、毒砂等）。目前研究显示铟主要赋存于闪锌矿中，但分布不均匀，含量变化从11×10-6至3900×10-6，平均761.15×10-6（周卫宁等，1987；杨锋，2009；伍永田，2009；罗卫，2009；皮桥辉，2015；胡家刚，2016；董从芳等，2017；唐源壑，2017；张含等，2019）。
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（2）岩浆-热液型（14个）。岩浆-热液型伴生铟矿床数量位居第二，占总矿床数量的24.5%，主要分布范围为中亚造山带、扬子地台和华夏地块（图2），规模从中型到大型不等。典型矿床有孟恩陶勒盖、大井、阿尔哈达、红旗岭、锯板坑等。其中以孟恩陶勒盖矿床最具有代表性，该矿床位于内蒙古大兴安岭与松辽沉降带接壤部位，矿体直接产于孟恩陶勒盖岩基中心部位一组近东西向断裂带内，形成时代为早侏罗世—中侏罗世（张炯飞等，2003；张乾等，2004），处于造山后伸展的构造背景（高飞，2018）。矿床共包含44个矿体，分布于西部、中部、东部3个矿段，铅矿石储量为0.17 Mt（品位为1%），锌矿石储量为0.37 Mt（品位为2.3%），伴生有Ag、Sn、In（500 t）和Cd（1800 t）（Zhang Qian et al.，2006）。矿石矿物主要为方铅矿、闪锌矿、黄铜矿。前人研究表明In、Cd均富集于闪锌矿中，Cd在3个矿段闪锌矿中富集程度相同，变化范围为0.18%~0.45%；In含量变化范围较大，从85×10-6至2660×10-6，并且在3个矿段中呈现自西向东w（In）依次降低的趋势，可能与闪锌矿中Fe的含量有关（张乾等，2004）。
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（3）海相火山岩型（6个）。海相火山岩型矿床又称为块状硫化物矿床，是铁、铜、铅、锌的主要来源，规模一般为小型至中型。该类型矿床仅占矿床总数的10.5%，零星分布于全国各地（图2）。其中，甘肃白银厂矿田小铁山Pb-Zn-Cu-S-Au-Ag-In-Cd-Ga-Ge-Tl-Se矿床研究程度最高，大地构造位置为秦祁昆造山带中段，矿床赋存于奥陶系海相火山岩中，形成时代为中奥陶世（472.6~468.1 Ma），处于弧后伸展的构造背景（梁婉秋，2014；董凯，2018）。小铁山矿床Cu、Pb、Zn矿石储量分别为0.1 Mt、0.33 Mt、0.55 Mt，In主要赋存于闪锌矿（0.01× 10-6~35.5×10-6）和黄铁矿（0.01×10-6~2.4×10-6）中（董凯，2018）。
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（4）叠加（复合/改造）型（5个）。叠加（复合/改造）型伴生铟矿床仅有5个，占总数的8.7%，零星分散在华北克拉通、扬子地台、华夏地块和喜马拉雅-青藏高原造山带（图2）。该类型的矿床规模一般为大型，后期遭受了岩浆、热液的叠加和改造。最典型的为老厂Ag-Pb-Zn-Mo-Cu矿床，位于三江成矿带昌宁-孟连裂谷盆地南部，关于成矿年龄前人观点不一，主要有燕山晚期到喜马拉雅早期（徐楚明等，1991；欧阳成甫等，1993），燕山期（范承钧，1985），海西期—燕山期（周凤禄，1991）。结合目前最新的成岩成矿年龄和相关研究，老厂矿床早期的火山喷发作用与铅锌矿化有关，后期受到了喜山期花岗斑岩的侵入叠加改造（龙汉生等，2009；李峰等，2010；叶霖等，2012）。构造背景为典型的陆内碰撞造山环境（叶霖等，2012）。该矿床的矿石总量为1.2 Mt，矿石品位为Pb2.8%，Zn 1.1%~7.3%，伴生Ag、In、Cd。该矿床中闪锌矿是In的最主要载体，含量变化范围为65.5×10-6~1576×10-6，平均为454.27×10-6，其中大部分闪锌矿中In含量高于100×10-6（Ye Lin et al.，2011；Chen Wei et al.，2018），初步估算老厂伴生In远景储量超过4000 t（罗艳碧等，2013）。
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（5）陆相火山岩型（2个）。陆相火山岩型矿床形成于浅地表，成矿深度主要在1 km，个别可达2 km，形成温度一般小于150℃，是金、银等贵金属的重要来源（李铁刚，2016）。我国陆相火山岩型伴生铟矿床共有2个，分别为内蒙古甲乌拉Pb-Zn-Ag-In-Cd和福建紫金山Cu-Au-In矿床。甲乌拉矿床位于大兴安岭北段，形成于晚侏罗世—早白垩世（154~122 Ma），构造背景为碰撞后伸展环境（曹艳华等，2020）。矿床保有资源储量矿石量为3.06 Mt，平均品位Pb1.94%，Zn 3.78%，伴生Cu、Ag、In（92 t）、Cd（1135 t）（牛斯达，2017）。主要矿石矿物为方铅矿、闪锌矿、黄铁矿、磁黄铁矿、黄铜矿，含In矿物为闪锌矿，In含量为13×10-6~160×10-6，平均值为66×10-6。紫金山矿床位于华夏陆块南侧的闽西南拗陷带，成矿时代为早白垩世（113~95 Ma），形成于岩石圈伸展的构造背景（毛景文等，2008）。矿床Cu金属量为2.3 Mt，Au金属量305 t（王少怀等，2009；张锦章，2013），具有上金下铜的矿化垂直分带特征。金属矿物主要为铜矿物和褐铁矿、针铁矿，In以独立矿物（硫铟铜矿）的形式存在于该矿床中，其In含量高达33.69%~44.42%，平均为40.79%，形成于相对还原和中高温环境下（王少怀等，2014）。
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（6）斑岩型（1个）。江西冷水坑Ag-Pb-Zn-Au-Cu-In-Cd矿床的主要成因类型为斑岩型（左力艳，2008），矿床位于扬子板块与华夏陆块拼接带南部，形成时代跨越晚侏罗世—早白垩世，成矿与燕山期花岗斑岩关系密切。矿石储量预计为4.3 Mt，Pb、Zn、Ag平均品位分别为2.11%、2.61%、204 g/t，伴生有Cd（13000 t）、In、Cu、Fe、Mn（王长明等，2011；Gong Xuejing et al.，2019）。矿石矿物主要有银矿物及银金矿物、硫化物、氧化物3大类，In与Cd主要赋存于闪锌矿中，In含量变化范围较大（0.21×10-6~671×10-6），指示了成矿温度由低温到高温的变化趋势（韩照信，1994），Cd在闪锌矿中分布比较均匀，含量为3070×10-6~9383×10-6。
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图1 中国伴生铟矿床地理位置分布图
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Fig.1 The geographic location distribution map of the indium-bearing deposits in China
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1 —谢尔塔拉Fe-Zn-In-Cd矿床；2—甲乌拉Pb-Zn-Ag-In-Cd矿床；3—孟恩陶勒盖Zn-Pb-Ag-In-Ga-Cd矿床；4—大井Cu-Sn-Pb-Zn-Ag-In-Cd矿床；5—三矿沟Fe-Cu-Au-Ag-Se-In-Ga-Cd矿床；6—朝不楞Fe-Bi-Ag-Sn-In-Cd-Ga矿床；7—阿尔哈达Pb-Zn-Ag-In-Cd-Ga矿床；8—查干敖包Fe-Zn-In-Cd矿床；9—翠宏山Fe-Mo-W-Zn-Pb-Cu-Ag-In-Cd矿床；10—二股西山Fe-Zn-Pb-Cu-In-Cd-Ga矿床；11—放牛沟Fe-Zn-S-In-Cd矿床；12—八家子Pb-Zn-Ag-Mo-In-Cd矿床；13—楼长沟Pb-Zn-In-Cd-Ga矿床；14—栖霞山Pb-Zn-In-Cd-Ga-Ge矿床；15—小茅山-吴宅Cu-Pb-Zn-Ag-In-Cd多金属矿床；16—丰山Cu-Au-Ag-Te-Tl-Se-In-Cd矿床；17—东岗山矿区Pb-Zn-Ag-In-Cd萤石矿床；18—乌岙Pb-Zn-In-Cd多金属矿床；19—冷水坑Ag-Pb-Zn-Au-Cu-In-Cd矿床；20—丁家山Pb-Zn-In-Cd矿床；21—岭头坪Au-Pb-Zn-Cu-In-Cd矿床；22—洛阳Fe-Mo-S-Zn-In-Cd矿床；23—中甲Fe-In-Cd矿床；24—锯板坑W-Sn-Cu-Pb-Zn-In-Cd矿床；25—仙人顶Pb-Zn-Ag-In-Cd矿床；26—铁屎坪As-In-Cd矿床；27—泡金山Sn-Pb-Zn-In-Cd矿床；28—柳塘岭Pb-Zn-In-Cd矿床；29—玛瑙山Fe-Mn-In-Cd矿床；30—红旗岭W-Sn-Pb-Zn-Mo-Bi-In-Cd矿床；31—野鸡尾W-Sn-Pb-Zn-In-Cd矿床；32—康家湾Pb-Zn-In-Cd矿床；33—龙塘Pb-Zn-In-Cd矿床；34—漂塘Pb-Zn-In-Cd矿床；35—七宝山S-Cu-Pb-Zn-Co-In-Cd矿床；36—长埔Sn-W-Mo-Pb-Zn-Ag-In-Cd矿床；37—吉水门Sn-Pb-Zn-Ag-In-Cd-S矿床；38—金子窝Sn-In-Cd矿床；39—水龙尾Pb-Zn-In-Cd矿床；40—甲龙Sn-Cu-In-Cd矿床；41—大厂Sn-In-Cd-Pb矿床；42—红石岩Pb-Zn-In-Cd矿床；43—都龙Sn-Pb-Cu-In-Cd矿床；44—白牛厂Ag-Sn-Pb-Zn-In-Cd矿床；45—个旧Sn-Cu-In-Ga-Ge-Cd矿床；46—钦甲Cu-Sn-In-Cd矿床；47—老厂Ag-Pb-Zn-Mo-Cu-In-Cd矿床；48—杉树林Pb-Zn-In-Cd矿床；49—茂租Pb-Zn-In-Cd矿床；50—德尔尼Cu-Zn-Co-S-Au-Ag-In-Cd-Ga矿床；51—白银厂（矿田）小铁山Pb-Zn-Cu-S-Au-Ag-In-Cd-Ga-Ge矿床；52—锡铁山Pb-Zn-S-Ag-Au-In-Cd-Ga-Ge矿床；53—彩霞山Pb-Zn-In-Cd矿床；54—赛什塘Cu-Pb-Zn-Au-Ag-S-Fe-In矿床；55—日龙沟Cu-Sn-Pb-Zn-In矿床；56—黄沙坪Pb-Zn-Ag-W-Sn-Au-Cu-Fe-In矿床；57—紫金山Cu-Au-In矿床
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1 —Xieertala Fe-Zn-In-Cd deposit; 2—Jiawula Pb-Zn-Ag-In-Cd deposit; 3—Mengentaolegai Zn-Pb-Ag-In-Ga-Cd deposit; 4—Dajing Cu-Sn-Pb-Zn-Ag-In-Cd deposit; 5—Sankuanggou Fe-Cu-Au-Ag-Se-In-Ga-Cd deposit; 6—Chaobuleng Fe-Bi-Ag-Sn-In-Cd-Ga deposit; 7—Aerhada Pb-Zn-Ag-In-Cd-Ga deposit; 8—Chaganaobao Fe-Zn-In-Cd deposit; 9—Cuihongshan Fe-Mo-W-Zn-Pb-Cu-Ag-In-Cd deposit; 10—Erguxishan Fe-Zn-Pb-Cu-In-Cd-Ga deposit; 11—Fangniugou Fe-Zn-S-In-Cd deposit; 12—Bajiazi Pb-Zn-Ag-Mo-In-Cd deposit; 13—Louchanggou Pb-Zn-In-Cd-Ga deposit; 14—Qixiashan Pb-Zn-In-Cd-Ga-Ge deposit; 15—Xiaomaoshan-Wuzhai Cu-Pb-Zn-Ag-In-Cd deposit; 16—Fengshanlijiawan Cu-Au-Ag-Te-Tl-Se-In-Cd deposit; 17—Donggangshan Pb-Zn-Ag-In-Cd fluorite deposit; 18—Wuao Pb-Zn-In-Cd multi-metal deposit; 19—Lengshuikeng Ag-Pb-Zn-Au-Cu-In-Cd deposit; 20—Dingjiashan Pb-Zn-In-Cd deposit; 21—Lingtouping Au-Pb-Zn-Cu-In-Cd deposit; 22—Luoyang Fe-Mo-S-Zn-In-Cd deposit; 23—Zhongjia Fe-In-Cd deposit; 24—Jubankeng W-Sn-Cu-Pb-Zn-In-Cd deposit; 25—Xianrending Pb-Zn-Ag-In-Cd deposit; 26—Tieshiping As-In-Cd deposit; 27—Paojinshan Sn-Pb-Zn-In-Cd deposit; 28—Liutangling Pb-Zn-In-Cd; 29—Manaoshan Fe-Mn-In-Cd deposit; 30—Hongqiling W-Sn-Pb-Zn-Mo-Bi-In-Cd deposit; 31—Yejiwei W-Sn-Pb-Zn-In-Cd deposit; 32—Kangjiawan Pb-Zn-In-Cd deposit; 33—Longtang Pb-Zn-In-Cd deposit; 34—Piaotang Pb-Zn-In-Cd deposit; 35—Qibaoshan S-Cu-Pb-Zn-Co-In-Cd deposit; 36—Changpu Sn-W-Mo-Pb-Zn-Ag-In-Cd deposit; 37—Jishuimen Sn-Pb-Zn-Ag-In-Cd-S deposit; 38—Jinziwo Sn-In-Cd deposit; 39—Shuilongwei Pb-Zn-In-Cd deposit; 40—Jialong Sn-Cu-In-Cd deposit; 41—Dachang Sn-In-Cd-Pb deposit; 42—Hongshiyan Pb-Zn-In-Cd deposit; 43—Dulong Sn-Pb-Cu-In-Cd deposit; 44—Bainiuchang Ag-Sn-Pb-Zn-In-Cd deposit; 45—Gejiu Sn-Cu-In-Ga-Ge-Cd deposit; 46—Qinjia Cu-Sn-In-Cd deposit; 47—Laochang Ag-Pb-Zn-Mo-Cu-In-Cd deposit; 48—Shanshulin Pb-Zn-In-Cd deposit; 49—Maozu Pb-Zn-In-Cd deposit; 50—De'erni Cu-Zn-Co-S-Au-Ag-In-Cd-Ga deposit; 51—Baiyinchang (Xiaotieshan) Pb-Zn-Cu-S-Au-Ag-In-Cd-Ga-Ge deposit; 52—Xitieshan Pb-Zn-S-Ag-Au-In-Cd-Ga-Ge deposit; 53—Caixiashan Pb-Zn-In-Cd deposit; 54—Saishitang Cu-Pb-Zn-Au-Ag-S-Fe-In deposit; 55—Rilonggou Cu-Sn-Pb-Zn-In deposit; 56—Huangshaping Pb-Zn-Ag-W-Sn-Au-Cu-Fe-In deposit; 57—Zijinshan Cu-Au-In deposit
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图2 中国伴生铟矿床的构造区带分布图（矿床编号同图1；底图据刘英超等，2022修改）
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Fig.2 Tectonic spatial distribution map of the indium-bearing deposits in China (the deposit numbers are the same as Fig.1, underlying graph is from Liu Yingchao et al., 2022)
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（7）受变质型（1个）。受变质型矿床是指先形成的矿床，后期又受到区域变质作用的影响和改造的矿床（沈其韩，2007）。甲龙Sn-Cu-In-Cd矿床是目前发现的唯一一个受变质型伴生铟矿床，该矿床位于江南造山带的西缘，成矿时代为421.9 Ma，赋存于新元古界地层中（岳志恒，2022）。矿石矿物为黄铜矿、锡石、磁黄铁矿、黄铁矿、闪锌矿等。金属Cu资源量为12806 t（品位为0.45%~0.70%），金属Sn资源量为3000 t（品位为0.2%~0.3%），除Cu、Sn外，In也达到了工业开采品位（Liu Jianping et al.，2018；向路，2021）。
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2 中国伴生铟矿床的分布特征
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中国伴生铟矿床分布极不均匀，主要集中于东北和华南地区，零星分散在中西部地区，主要省份包括黑龙江、内蒙古、湖南、福建、广东、广西、江苏、江西、青海、云南等（图1），其中内蒙古、云南、广西、广东四省的铟储量占中国总量的80%以上（涂光炽等，2004）。
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从构造环境来看，铟矿床集中分布于中亚造山带东段、扬子地台西侧和南部以及华夏陆块，少数分布于华北克拉通、喜马拉雅-青藏高原造山带和柴达木盆地。其中，以矽卡岩型伴生铟矿床分布范围最广，多沿板块的边界或是走滑断裂带分布。其次为岩浆-热液型伴生铟矿床，集中分布于中亚造山带、华北克拉通、扬子地台和华夏陆块腹部。海相火山岩型和叠加改造型伴生铟矿床主要分布于造山带与大洋-大陆板块的边缘。陆相火山岩型、斑岩型和受变质型由于数量较少而没有显示出明显的分布规律特征，零散分布于中亚造山带、扬子地台和华夏陆块。
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按照伴生铟矿床的储量分布特征来看，目前只有19个矿床拥有铟、镉、镓的储量数据（表2）。依照铟、镉、镓的矿产资源储量规模划分标准：铟大型≥500 t、铟中型100~500 t、铟小型＜100 t；镉大型≥3000 t、镉中型500~3000 t、镉小型＜500 t；镓大型≥2000 t、镓中型400~2000 t、镓小型＜400 t。桂北-滇南成矿带的岩浆-热液成因锡石-硫化物矿床多形成铟的大型矿床（张乾等，2008；Werner et al.，2017），如广西大厂铟探明储量超过8000 t，云南都龙铟保有储量超过6000 t（徐净等，2018），云南个旧铟储量超过4000 t（Zhang Qian et al.，2005），云南澜沧老厂远景储量超过4000 t（罗艳碧等，2013）。这几个矿床除了铟超常富集外，镉含量也远高于其他地区（表2），因此扬子地台西南缘是中国乃至世界罕见的铟和镉稀散金属的聚集区（Hu Ruizhong et al.，2012，2017）。
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相比而言，其他地区只有少数几个矿床中的铟储量达到大型规模，如大兴安岭南段的孟恩陶勒盖（超过500 t）和大井（768 t）（Zhang Qian et al.，2006；Ishihara et al.，2008），华夏陆块南部的中甲（约569 t）（毛光武，2011），扬子地台南部的野鸡尾（580 t）和七宝山（659 t；中国矿床发现史·湖南卷，1996）。同时，已知储量数据的8个伴生铟矿床镉储量均超过500 t，达到中型规模；但是镓的储量均不高，目前只有湖南野鸡尾W-Sn-Pb-Zn-In-Cd矿床的Ga储量达到中型，其余均为小型（表2）。
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3 中国伴生铟矿床的形成时代
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中国伴生铟矿床可以形成于从寒武纪到古近纪的各个地质历史时期（附表2、图3），其中中生代（三叠纪、侏罗纪和白垩纪）占绝大多数，该时期形成的伴生铟矿床中铟资源量占总量的85%。古近纪和中生代之前的伴生铟矿床数量相对较少：云南老厂Ag-Pb-Zn-Mo-Cu-In-Cd矿床是目前发现形成时代最新（50~43 Ma）的伴生铟矿床，属叠加（复合/改造）型，其形成可能与后期古近纪含矿岩浆-热液的叠加改造有关。矽卡岩型、岩浆-热液型、海相火山岩型和受变质型伴生铟矿床均有早于中生代的伴生铟矿床，时代最老的是位于青海省的锡铁山Pb-Zn-S-Ag-Au-In-Cd-Ga-Ge矿床，形成于514~486 Ma的寒武纪。
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（1）矽卡岩型（190个年龄数据）。该类型矿床的成岩成矿作用峰期为中生代，最主要的形成时代为白垩纪（143~69 Ma），其次为侏罗纪（200~146 Ma），少量形成于三叠纪（254~205 Ma；图3a），唯一形成于志留纪的矿床是广西的钦甲Cu-Sn-In-Cd矿床。福建洛阳Fe-Mo-S-Zn-In-Cd矿床和湖南黄沙坪Pb-Zn-Ag-W-Sn-Au-Cu-Fe-In矿床的成岩成矿年龄均跨越两个时代。其中，福建洛阳矿床成岩年龄为154~153 Ma和132~129 Ma（附表2），显示该矿区存在晚侏罗世和早白垩世两期岩浆活动，134~133 Ma的成矿年龄显示成矿作用与早白垩世岩浆活动更加密切（张达等，2012；宇腾达，2017）。湖南黄沙坪矿床的成矿年龄主要集中在晚侏罗世（159~153 Ma），仅有单个闪锌矿Rb-Sr等时线年龄为143 Ma，说明该地区成矿作用以晚侏罗世为主，卢友月等（2015）将上述早白垩世年龄解释为晚侏罗世钨锡矿化延续和铜铅锌矿化增强。
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（2）岩浆-热液型（53个年龄数据）。岩浆-热液型绝大多数成岩成矿年龄集中于中生代，少数形成于石炭纪和二叠纪（图3b）。内蒙古大井Cu-Sn-Pb-Zn-Ag-In-Cd矿床目前只有锆石U-Pb年龄数据，年龄数据跨越4个时代，二叠纪、三叠纪、侏罗纪和白垩纪。江思宏等（2012）认为该矿区存在着海西晚期、印支早期、燕山早期、燕山中期四期岩浆活动，而晚侏罗世—早白垩世是其主要的成矿期（廖震等，2012；江思宏等，2012；刘铭涛等，2019）。湖南红旗岭W-Sn-Pb-Zn-Mo-Bi-In-Cd矿床目前仅有的2个年龄数据显示其可能形成于晚侏罗世（154 Ma）和早白垩世（143 Ma），结合区域上柿竹园矿集区158~154 Ma的成岩成矿年龄范围（郭春丽等，2015），红旗岭矿床很可能形成于晚侏罗世。
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（3）海相火山岩型（15个年龄数据）。该类型矿床的形成时代不同于其他6种类型，没有出现中生代及以后的年龄数据（图3c），表明自二叠纪之后就未形成或者尚未发现此类型的矿床。其中青海德尔尼Cu-Zn-Co-S-Au-Ag-Se-In-Cd-Ga矿床目前仅有4个年龄数据，且跨度较大（345~296 Ma）。
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（4）叠加（复合/改造）型（7个年龄数据）。已有数据显示该类型矿床形成于侏罗纪及以后（图3d）。福建中甲Fe-In-Cd矿床目前已有的4个年龄数据显示其形成于早侏罗世（辉钼矿Re-Os年龄为196~193 Ma；张达等，2003）和晚白垩世（锆石U-Pb年龄为98.5 Ma；杨祖龙等，2008），该矿床具有复合成因，前期经历了海底火山喷发沉积过程，后期又受到高温岩浆热液的改造。
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（5）陆相火山岩型（40个年龄数据）。陆相火山岩型伴生铟矿床的形成时代集中于中晚侏罗世—早白垩世。已有年龄数据显示，甲乌拉伴生铟矿床的成岩年龄为152~124 Ma，成矿年龄为153~132 Ma。紫金山伴生铟矿床的成岩年龄范围集中于中晚侏罗世（168~146 Ma；附表2）和晚白垩世（113~95 Ma；附表2），谢其锋等（2019）认为其中成矿作用与早白垩世岩浆活动密切相关。
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（6）斑岩型（30个年龄数据）。冷水坑斑岩型伴生铟矿床的成岩年龄跨度较大（168~134 Ma），表明岩浆活动时间较长。已有的两个成矿年龄数据为127 Ma和163 Ma。
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（7）受变质型（1个年龄数据）。甲龙受变质型伴生铟矿床的唯一一个锡石U-Pb年龄表明其形成于422 Ma。
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4 铟的替代机制
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铟的物理、化学性质与锌具有极高的相似性，决定了其能够以类质同象的方式赋存于闪锌矿中（ZnS；涂光炽等，2004）。闪锌矿是目前已知矿物中In的最佳载体矿物（最高含量高达24.73%；Bauer et al.，2019），其在{111}方向的堆积层错和螺旋位错的晶格缺陷是诱导In进入闪锌矿中的主要原因。具体表现为In与其他微量元素（如Cu、Ag、Sn）共同替代闪锌矿中的Zn（Cook et al.，2009，2012; Ciobanu et al.，2011；Xu Jing et al.，2020b），替代方式为In3++Cu+→2Zn2+和In3++Sn2++Ag+→3Zn2+。例如，Murakami et al.（2013）通过对日本Akenobe锡多金属矿床和中国云南都龙锡多金属矿中闪锌矿的研究发现，两种矿床中Cu均与In、Ag呈正相关关系，但这些元素并没有表现出与Sn的相关性，因此In最有可能是以In3++Cu+/Ag+→2Zn2+的方式替代了闪锌矿中的Zn。局部富铟部位可以有少量的晶格空位，与上述阳离子一并构成有效的置换机制（Cook，2009; Ciobanu et al.，2011；Belissont et al.，2014），例如In3++Sn3++□（空位）→3Zn2+、In3++Sn4++（Cu、Ag）++□（空位）→4Zn2+。Xu Jing et al.（2020a，2020b）通过激光电感耦合等离子体质谱（LA-ICP-MS）、聚焦离子束扫描电镜（FIB-SEM）、球差投射电镜（AC-TEM）等原位微区技术手段，对云南都龙锡多金属矿床中的富铟闪锌矿开展了纳米尺度的矿物学研究，发现该矿床中铟替代Zn的主要机制为In3++Cu+→2Zn2+、In3++Sn2++Ag+→3Zn2+和In3++Sn4++（Cu、Ag）++□（空位）→4Zn2+；异常富铟闪锌矿的理论化学式为[（Cu，In，Zn）3（Zn0.5Fe0.5）]4S4，在局部特别富In的部位有立方晶系闪锌矿向四方晶系硫铟铜矿（CuInS2）转变的现象。
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图3 中国7种成因类型伴生铟矿床的形成年龄直方图（a~g，数据来源于附表2）
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Fig.3 Age histograms of China seven types of the indium-bearing deposits （a~g, data are derived from Appendix 2）
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Lerouge et al.（2017）对法国Beauvoir、Montbelleux、Abbaretz和西班牙Magros、Marcofán锡多金属矿床中的锡石进行了电子探针成分分析和结构公式计算，得出Fe2+和Fe3+与Nb、Ta以类质同象方式替代锡石中Sn的理想机制为：Fe2++2（Nb，Ta）5+↔3（Sn，Ti）4+、Fe3++（Nb，Ta）5+↔2（Sn，Ti）4+，并以此为基础推导出In与Fe相结合替代Sn的机制为（In，Fe）3++（Nb，Ta）5+→2（Sn，Ti）4+，而且可以产生进一步的置换Fe2++（Nb，Ta）5+→In3++（Sn，Ti）4+，说明Nb、Ta离子是影响In元素在锡石中富集的重要因素。
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在检测闪锌矿中In含量时，常发现其同时也富集3种元素Cd、Ga、Ge，因此本文也将这3种元素在闪锌矿中的替代机制进行总结。Cd和Zn同属IIB族，二者具有非常相似的离子半径和四面体共价半径，并且均为亲硫元素（涂光炽等，2004）。Ga、In都具有与Zn相似的（弱）亲铜性（Vershkovskaya，1966；Smith et al.，1978），Ge具有与Zn相似的亲硫性（Höll et al.，2007）。相似的物理、化学性质使得Cd、Ga、Ge与Zn具有相似的地球化学行为，因而极易以类质同象方式替代闪锌矿中的Zn，其中Cd甚至能够以Cd2+→Zn2+的方式直接替代Zn（叶霖等，2005；Cook et al.，2009），这种高效的替代方式使得成矿流体中的Cd能够最大限度地进入闪锌矿。除Cd之外，Ga、Ge、In是通过结合其他离子共同替代Zn2+从而进入闪锌矿的晶格。但是，Ge替代Zn的机制目前尚未统一，包括Ge2+或Ge4+简单替代Zn2+（±Fe2+）的模式，例如Ge2+→Zn2+（Cook et al.，2009; Ye Lin et al.，2011）、Ge4++□（空位）→2Zn2+（Belissont et al.，2016）、Ge4++□（空位）→Zn2++Fe2+（Cook et al.，2015），或者以Ge4+结合Cu或Ag耦合替代Zn2+的机制，Ge4++2Cu++Cu2+→4Zn2+（Johan，1988）、Ge4++2Ag+→3Zn2+（Belissont et al.，2014）、Ge4++2Cu+→3Zn2+（Belissont et al.，2016）。
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5 铟的独立矿物
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迄今为止全球发现的铟独立矿物共计19种，其中尚有3种矿物未被命名（表3）。
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在目前已发现的铟独立矿物中，相较于多数矿物仅在特定的矿床中被报道，硫铟铜矿（In含量47%）是发现最多的铟独立矿物。Picot（1963）在法国Charrier W-Sn矿床中首次发现硫铟铜矿，之后在我国各地也均有报道。例如，在我国青海赛什塘-日龙沟矽卡岩型Cu-Sn-In矿床中，富斑铜矿矿石存在1~4 μm的硫铟铜矿（图4c; Liu Jianping et al.，2016）；福建紫金山Au-Cu-In矿床（王少怀等，2014）和湖南香花岭Sn-Nb-Ta-In矿床（夏金龙等，2022）中也含有少量硫铟铜矿。
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西藏班公湖-怒江成矿带矽卡岩型Cu-Fe-In矿床中含有直径4~20 μm羟铟石（In（OH）3）和6~10 μm自然铟（In），后者可由前者经脱水转变而来（图4a、b；赵元艺等，2010；刘妍等，2010）。
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伊逊矿、大庙矿最早由於祖相（1997a，1997b）于1972年、1976~1977年在河北寻找铂矿时发现，这两种新矿物最终于1996年经国际新矿物与矿物命名委员会审查通过（Mandarino，1996）。河北石榴子石角闪石辉石岩含钴、铜的铂矿脉中，出现直径1000~2000 μm小圆球状的伊逊矿（Pt3In），与大庙矿（PtIn2）呈紧密连晶（图4d；於祖相， 1997b）。
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图4 中国几个典型伴生铟矿床中铟的独立矿物
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Fig.4 Indium independent minerals from representative indium-bearing deposits in China
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（a）—西藏班公湖-怒江成矿带透射光下红色闪锌矿间碳酸盐矿物中包裹的等轴晶系矿物羟铟石（赵元艺等，2010）；（b）—自然铟（赵元艺等，2010）；（c）—青海赛什塘-日龙沟矿床中的硫铟铜矿（Liu Jianping et al.，2016）；（d）—伊逊矿，外围包有一圈大庙矿（於祖相，1997b）
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(a) —isometric-granular mineral in carbonatite minerals which is distributed among sphalerite crystals, and the sphalerite crystals are red under the transmitted light of Bangong lake-Nujiang river metallogenic belt and adjacent regions in Tibet (Zhao Yuanyi et al., 2010) ; (b) —native indium (Zhao Yuanyi et al., 2010) ; (c) —roquesite from Qing hai Saishitang-Rilongggou ore field deposit (Liu Jianping et al., 2016) ; (d) —yixunite, surrounded by a ring of damiaoite (Yu Zuxiang, 1997b)
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6 铟的超常富集规律
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6.1 铟在岩浆中的富集规律
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铟在地壳、地幔、地核中的丰度分别为0.14×10-6、18±3×10-9、0.5×10-6（牟保磊，1999；Witt-Eickschen et al.，2009）。铟属于亲铜、亲硫元素，其化合价为+1价和+3价，在自然界中常以In3+阳离子形式存在，其正三价离子半径为0.81 nm，与Sn4+（0.71 nm）、Zn2+（0.74 nm）、Fe2+（0.72 nm）、Cu2+（0.72 nm）、Sb2+（0.76 nm）相近（涂光炽等，2004）。
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铟具有亲岩浆性（Schwarz-Schampera et al.，2002；李晓峰等，2010；Ishihara et al.，2011），但是铟在岩浆岩中的含量分布具有差异，在酸性岩、中性岩、基性岩和超基性岩中的含量分别为0.26×10-6、0.06×10-6、0.22×10-6、0.01×10-6（迟清华等，2007）。Ivanov（1969，转引自涂光炽等，2004）研究发现岩浆岩中的铟与（Fe）含量呈正相关，这一结论得到了牟保磊（1999）和涂光炽等（2004）的认同。Gion et al.（2019）采用概念模型方法计算发现，随着镁铁质矿物在岩浆中比例增高，铟矿化的可能性降低，说明镁铁质岩浆加入中酸性岩浆房不利于铟的富集。王大鹏等（2019）通过对薄竹山花岗岩及其包体的黑云母进行研究，发现铟随岩浆结晶分异逐步发生富集，说明铟含量高低与岩浆分异程度有关。同时，研究表明我国扬子地台西南缘的大型富铟矿床，例如个旧、都龙、大厂、白牛厂等，都与高分异花岗岩具有成因联系（李玉帮等，2014；赵震宇，2017；郭佳，2019）。
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挥发分同样对铟的富集具有重要影响。其中，氟含量对铟在熔体中的富集具有一定的控制作用（Simons et al.，2017），并且富氟的花岗质岩浆往往显现出富含钨、锡、钼、铋等元素的高分异特征。Seward et al.（2000）则通过实验得出铟在岩浆-热液中主要是以InCl-和InClOH+等络合物形式迁移，温度越高In3+离子与氯络合物结合数量越多，在300~350℃时InCl-含量达到最高。
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6.2 铟在矿床中的富集规律
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通常认为，In以分散状态存在于矿物中，在自然界中很难形成真正意义上的独立矿床，但是却可以大量富集于特定类型的矿床和矿物中（涂光炽等，2004）。张乾等（2003）研究发现富铟矿床主要是富锡的铅锌硫化物矿床，铟主要赋存于闪锌矿中，平均含量为8×10-6~1390×10-6，远高于锡石（6×10-6~42×10-6）、黄铁矿（0.2×10-6~8×10-6）、黄铜矿（0.7×10-6~8×10-6）、磁黄铁矿（1×10-6~30×10-6）和毒砂（0.4×10-6~7×10-6）。Ishihara et al.（2011）通过对Bolivian的锡多金属矿床进行研究，提出铟优先富集于闪锌矿中，其次才会富集于含锡硫化物和含银硫酸盐中。Lerouge et al.（2017）调查Variscan Belt西部时，发现黝锡矿中铟含量最高（~3000×10-6），其次为黄铜矿（~2800×10-6），黄铁矿（~1490×10-6），毒砂（~740×10-6），闪锌矿（~700×10-6）。英格兰西南部地区虽然部分闪锌矿中铟含量可达1.42%，但是大部分铟仍主要富集于黄铜矿中（~2200×10-6）（Andersen et al.，2016）。Pavlova et al.（2015）通过研究发现俄罗斯远东地区的富锡硫化物矿石中锡石的铟含量可达40×10-6~485×10-6，说明锡石同样也可以表现出富铟特征。
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受研究程度的制约，我国伴生铟矿床中各类硫化物和锡石中铟含量以电子探针和LA-ICP-MS数据为主，目前只有3个矿床开展了扫描电镜、透射电镜和离子探针研究（附表3）。基于统计数据，矽卡岩型和岩浆-热液型伴生铟矿床研究程度最高，积累的数据量也最多；海相火山岩型、叠加（复合/改造）型、陆相火山岩型和斑岩型矿床数据相对较少，其中陆相火山岩型矿床仅有铟、镉、镓数据，受变质型暂且无数据。
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结果显示（表4）闪锌矿是铟最主要的赋存矿物，其中铟含量最高可达101300×10-6，平均值相对铟的地壳平均丰度（0.14×10-6）的富集系数为8622.43。其次，富铟矿物为锡石和黝锡矿（表4），但数据仅来源于扬子地台西南缘的几个富铟锡石-硫化物矿床（甲龙、大厂、都龙），尚缺乏更全面、全国性的数据资料。大多数情况下黝锡矿中铟含量高于锡石（图5a、c），可见In在含锡矿物中更倾向进入含锡的硫化物而不是氧化物。从目前已有数据来看，其他7种硫化物的铟最高含量相较于闪锌矿低100个数量级，变化范围从0.01×10-6到1305.44×10-6（图5），依次为黄铜矿→辉钼矿→方铅矿→黄铁矿→毒砂→磁黄铁矿→磁铁矿（表4）。黄铜矿铟含量相对较高且较集中，方铅矿、黄铁矿和磁铁矿的铟含量较低且分散（图5a~e）。毒砂、辉钼矿、磁黄铁矿由于测试数据较少而并没有展示出明显的规律性。闪锌矿、黄铁矿和方铅矿测试数据显示出In与Cu、Cd和Ga具有明显的正相关性（图5c~e），其中黄铁矿还同时显示In与Zn具有负相关关系（图5a）。
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图5 中国各类硫化物中In与Zn、Fe、Cu、Cd、Ga、Ge的相关性图解
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Fig.5 Relationship between In and Zn, Fe, Cu, Cd, Ga and Ge in various sulfides in China
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数据来源：周卫宁等，1987；周天苗等，1988；王玉汪等，2002；张乾等，2004；高晓理，2006；韩世清，2006；刘文周，2009；罗卫，2009；孟祥金等，2009；伍永田，2009；杨锋，2009；李晓峰等，2010；承斯，2011；付强，2011；毛光武，2011；Ye Lin et al.，2011；卢燃，2012；王末等，2012；张荣伟，2013；张春茂，2013；陈贤，2015；Li Yubang et al.，2015；李玉帮，2015；皮桥辉，2015；胡家刚，2016；Liu Jianping et al.，2016，2017；于海华，2016；董从芳等，2017；冯玉龙等，2017; Liu Jianping，2017；唐源壑，2017；叶霖等，2017；赵飞，2017；Chen Wei et al.，2018；董凯，2018；杨松平等，2018；Gong Xuejing et al.，2019；李顺达，2019；陶琰等，2019；吴建标等，2019；尹文杰等，2019；张含，2019；牛浩斌等；2020；朱悦彰等，2020；李欢等，2021；刘建平等，2021; Zhao Yuehua et al.，2021，2022；Qi Youqiang et al.，2022；田静等，2022；岳志恒，2022
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Data sources: Zhou Weining et al.，1987；Zhou Tianmiao et al.，1988；Wang Yuwang et al.，2002；Zhang Qian et al.，2004；Gao Xiaoli，2006；Han Shiqing，2006；Liu Wenzhou，2009；Luo Wei，2009；Meng Xiangjin et al.，2009；Wu Yongtian，2009；Yang Feng，2009；Li Xiaofeng et al.，2010；Cheng Si，2011；Fu Qiang，2011；Mao Guangwu，2011；Ye Lin et al.，2011；Lu Ran，2012；Wang Mo et al.，2012；Zhang Rongwei，2013；Zhao Chunmao，2013；Chen Xian，2015；Li Yubang et al., 2015；Li Yubang, 2015; Pi Qiaohui，2015；Hu Jiagang，2016；Liu Jianping et al.，2016, 2017, 2021；Yu Haihua，2016；Dong Congfang et al.，2017；Feng Yulong et al., 2017；Liu Jianping，2017; Tang Yuanhe，2017；Ye Lin et al.，2017；Zhao Fei，2017；Chen Wei et al.，2018；Dong Kai，2018；Yang Songping et al.，2018; Gong Xuejing et al., 2019; Li Shunda，2019；Tao Yan et al.，2019；Wu Jianbiao et al.，2019；Yin Wenjie et al.，2019；Zhang Han，2019；Niu Haobin et al.，2020; Zhu Yuezhang et al.，2020；Li Huan et al.，2021；Zhao Yuehua et al.，2021, 2022；Qi Youqiang et al., 2022; Tian Jing et al.，2022; Yue Zhiheng，2022
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鉴于闪锌矿是最主要的赋铟矿物，本研究将7类伴生铟矿床（受变质型没有相关数据）中闪锌矿的铟富集程度进行了对比（图6），矽卡岩型伴生铟矿床中闪锌矿的铟含量最高，其次为叠加改造型，中位数分别为600×10-6和532×10-6，这两类伴生铟矿床中闪锌矿的铟含量明显高于其他类型。虽然岩浆-热液型、陆相火山岩型、斑岩型伴生铟矿床中闪锌矿铟含量低于前两类，但是仍有半数以上的闪锌矿铟含量达到了100×10-6，表明这3类伴生铟矿床也具有一定的铟资源潜力。而海相火山岩型伴生铟矿床中闪锌矿铟含量最低，即便是研究程度最高的白银厂矿田小铁山矿床，其闪锌矿中铟含量最高也仅有35.1×10-6。
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将7类伴生铟矿床的In含量与Zn、Fe、Cu、Cd、Ga、Ge元素进行相关性分析（图7），发现各类伴生铟矿床中In与Zn、Ge没有相关性（图7a、b），而In随Cu、Ga含量增加呈现出增加的趋势，暗示In3+离子与Cu和Ga阳离子共同替代闪锌矿中的Zn2+离子（In3++Cu+→2Zn2+、In3++Ga3+→3Zn2+）（图7c、d）（Cook et al.，2009；李云刚等，2020）。同时，闪锌矿也是Cd的主要赋存矿物，其Cd含量最高可达25876.71×10-6，平均值为3507.21×10-6，相对于地壳平均丰度富集了23381.42倍（表4）。而Ga和Ge主要富集于方铅矿中，在方铅矿中最高含量分别可达13790×10-6和5670×10-6，平均值分别为764.15×10-6和1225.64×10-6（表4）。
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图6 中国各类伴生铟矿床闪锌矿中In含量对比
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Fig.6 Comparison of In contents in sphalerite from seven types of the indium-bearing deposits in China
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数据来源：童潜明，1984；周卫宁等，1987；周天苗等，1988；赵一鸣等，1997；王玉汪等，2002；张乾等，2004；高晓理，2006；韩世清，2006；刘文周，2009；罗卫，2009；孟祥金等，2009；伍永田，2009；杨锋，2009；李晓峰等，2010；承斯，2011；付强，2011；毛光武，2011；Ye Lin et al.，2011；公凡影，2012；卢燃，2012；王末等，2012；张羽旭等，2012；张荣伟，2013；张春茂，2013；陈贤，2015；Li Yubang et al.，2015；李玉帮，2015；齐有强等，2015；皮桥辉，2015；陈伟，2016；胡家刚，2016；李铁钢，2016；Liu Jianping et al.，2016，2017；Niu Sida et al.，2016；于海华，2016；董从芳等，2017；冯玉龙等，2017；柯亮亮，2017；冷成彪等，2017；梁峰，2017；Liu Jianping，2017；唐源壑，2017；叶霖等，2017；赵飞，2017；陈鹏飞，2018；Chen Wei et al.，2018；董凯，2018；杨松平等，2018；Gong Xuejing et al.，2019；李顺达，2019；石得凤等，2019；陶琰等，2019；吴建标等，2019；尹文杰等，2019；张含，2019；韩颖霄，2020；牛浩斌等，2020；朱悦彰等，2020；李欢等，2021；刘建平等，2021；Zhao Yuehua et al.，2021，2022；Qi Youqiang et al.，2022；田静等，2022；岳志恒，2022
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Data sources: Tong Qianming, 1984; Zhou Weining et al., 1987; Zhou Tianmiao et al.，1988; Zhao Yiming et al.，1997; Wang Yuwang et al.，2002; Zhang Qian et al.，2004; Gao Xiaoli，2006; Han Shiqing，2006; Liu Wenzhou，2009; Luo Wei，2009; Meng Xiangjin et al.，2009; Wu Yongtian，2009; Yang Feng，2009; Li Xiaofeng et al.，2010; Cheng Si，2011; Fu Qiang，2011; Mao Guangwu，2011; Ye Lin et al.，2011; Gong Fanying，2012; Lu Ran，2012; Wang Mo et al.，2012; Zhang Yuxu et al.，2012；Zhang Rongwei，2013; Zhang Chunmao，2013; Chen Xian，2015; Li Yubang et al.，2015; Li Yubang，2015; Qi Youqiang et al.，2015; Pi Qiaohui，2015; Chen Wei，2016; Hu Jiagang，2016; Li Tiegang，2016; Liu Jianping et al.，2016, 2017, 2021; Niu Sida et al.，2016; Yu Haihua，2016; Dong Congfang et al.，2017; Feng Yulong et al.，2017; Ke Liangliang，2017; Leng Chengbiao et al.，2017; Liang Feng，2017; Liu Jianping，2017; Tang Yuanhe，2017; Ye Lin et al.，2017; Zhao Fei，2017; Chen Pengfei，2018; Chen Wei et al.，2018; Dong Kai，2018; Yang Songping et al.，2018; Gong Xuejing，2019; Li Shunda，2019; Shi Defeng et al.，2019; Tao Yan et al.，2019; Wu Jianbiao et al.，2019; Yin Wenjie et al.，2019; Zhang Han，2019; Han Yingxiao，2020; Niu Haobin et al.，2020; Zhu Yuezhang et al.，2020; Li Huan et al.，2021; Zhao Yuehua et al.，2021, 2022; Qi Youqiang et al.，2022; Tian Jing et al.，2022; Yue Zhiheng，2022
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图7 中国各类伴生铟矿床闪锌矿中In与Zn、Fe、Cu、Cd、Ga、Ge的相关性图解（数据来源同图6）
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Fig.7 Relationship between In and Zn, Fe, Cu, Cd, Ga and Ge in sphalerite from seven kinds of indium-bearing deposits in China （the data source is the same as Fig.6）
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铟与铁、镉具有特殊的相关性（图7e~i）。当铁含量＜10%时，闪锌矿中铟随铁含量增加呈现增长趋势；当铁含量＞10%时，铟随铁含量升高而降低，说明闪锌矿中的铁含量对铟的富集具有重要影响（图7e、f）。虽然只搜集到部分岩浆-热液型、叠加改造型、矽卡岩型矿床中闪锌矿的In和Cd数据，但仍能够显示出In与Cd具有相关性。闪锌矿中镉的含量在0.1×10-6~1×10-6时，In与Cd呈负相关关系（图7h）。Dill et al.（2013）认为闪锌矿中Cd含量在0.2%~0.6%时有利于铟的大量富集，并以此提出了“铟窗效应”，而实际上镉元素并不直接影响铟的富集，“铟窗效应”本质上是由闪锌矿的晶格变化所造成的：在Cu-Zn-Cd体系中，当硫逸度和温度降低时，铟寄主矿物的晶体形态和晶格参数会发生变化，如闪锌矿由立方晶系转变为四方晶系的硫铟铜矿，从而实现铟的超常富集，而镉元素的含量只是这种晶格变化的直观表现。从图7i可以看出，我国伴生铟矿床确实存在着这种“铟窗效应”，但是仅存在于矽卡岩型伴生铟矿床中，其中部分矽卡岩型伴生铟矿床铟含量达到了10000×10-6~100000×10-6，而其余6类矿床并没有在含量上表现出明显的变化，这可能说明“铟窗效应”对于矿床类别具有选择性。
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元素之间的相关性或许并不是唯一制约闪锌矿中铟含量高低的因素，Bauer et al.（2019）在研究德国Hämmerlein矽卡岩型矿床时，通过矿物成分和结构将该矿床中的闪锌矿分为两类，其中呈不规则状的IIa型闪锌矿中铟含量最高，其次为呈立方结构的IIc型闪锌矿。同样，Xu Jing et al.（2020a）按照矿物结构、粒度、组合、成分将都龙矿床中闪锌矿划分为4类，其中I型闪锌矿和II型闪锌矿中铟含量远高于其他类型的闪锌矿。以上研究说明并不是每一类闪锌矿都具有富铟特征，闪锌矿中铟的富集可能需要一定的物理化学条件（李晓峰等，2020），这也许是为什么各类型伴生铟矿床中闪锌矿中铟含量变化大的原因。而造成铟在不同类型闪锌矿之间选择性富集现象的关键因素需要进一步研究。
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7 铟的研究展望
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目前，已经基本查明我国伴生铟矿床的基本特征，但是对绝大多数矿床的研究尚处于起步阶段，无论成矿理论，还是资源家底都亟需进一步开展工作，集中体现在以下几个方面：
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（1）铟的富集机理和成矿机制尚不明确。对In和Cd、Ga、Ge元素在源、运、储成矿精细过程的认识不足，导致目前远未形成一个完整的理论体系。由此进一步导致了对这些稀散金属富集过程认识的困难，相关成矿规律的探讨更是难以进行。此外，更需要进一步探索我国是否拥有其他富铟成矿区/带，是否具有独立铟矿床，以及伴生/独立铟矿床是否可以形成于其他地质历史时期，从矿物→矿床→矿区/带尺度逐步揭秘铟的成矿机制。
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（2）铟的赋存状态尚需更高精度的技术手段来揭示。通过对57个伴生铟矿床文献中涉及的技术手段总结，发现绝大多数研究是基于野外、镜下观察、电子探针和LA-ICP-MS。电子探针分析所得数据精度不高，在此基础上进行储量评估将会出现较大误差。目前，只有七宝山矿床、都龙矿床拥有少量FIB-SEM、AC-TEM、离子探针数据，对其他55个矿床的研究程度尚浅。利用更高端的技术手段对铟的赋存形式和矿物中铟含量进行研究，需要找到更合适的样品以及付出更加艰辛的努力。
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（3）对伴生铟矿床中关键金属的“家底”尚未摸清。受前两个原因的制约，目前对In、Cd、Ga、Ge的储量评价工作尚且薄弱，只有19个（约1/3）矿床拥有品位和储量数据，其余暂为空白。这19个矿床为谢尔塔拉、孟恩陶勒盖、大井、三矿沟、朝不楞、翠宏山、二股西山、丰山、冷水坑、中甲、红旗岭、野鸡尾、七宝山、甲龙、大厂、都龙、个旧、老厂、德尔尼。因此，亟需对更多矿床开展精细的矿物分析，将数据转换成相应的品位和储量，建立起相关的更庞大和精确的数据库。
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附件：本文附件（附表1~3）详见http://www.geojournals.cn/dzxb/dzxb/article/abstract/202311091?st=article_issue
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左力艳. 2008. 江西冷水坑斑岩型银铅锌矿床成矿作用研究. 中国地质科学院博士学位论文.
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摘要
铟（In）是21世纪重要的紧缺战略性矿产，对国家稳定、发展和提升国际竞争力具有重要意义。中国拥有全球最丰富的铟资源，但尚未发现铟的独立矿床，目前已知的57个伴生铟矿床兼有镉（Cd）、镓（Ga）、锗（Ge）的资源潜力。本文在详细梳理所有伴生铟矿床的区域分布、成因类型、形成时代、赋存矿物、独立矿物和富集规律的基础上，总结了铟成矿作用的研究现状和发展方向。统计发现：我国伴生铟矿床高度集中于中亚造山带东段和华南地区；可划分为7种成因类型，包括矽卡岩型、岩浆-热液型、海相火山岩型、陆相火山岩型、叠加（复合/改造）型、斑岩型和受变质型；7类矿床中，铟无一例外主要赋存于闪锌矿中，作为副产品被回收；85%的伴生铟矿床形成于中生代，古近纪和中生代之前的矿床数量较少。目前全球已发现了19种铟独立矿物，我国报道了其中的5种。硫铟铜矿（CuInS2）是我国最常见的铟独立矿物，其余的铟独立矿物如自然铟，羟铟矿等仅出现在特定的伴生铟矿床中。目前研究多关注扬子地台西南缘的矽卡岩型伴生铟矿床，而对散布于全国各地其他6类伴生铟矿床的研究尚处于起步阶段。这在很大程度上限制了对铟富集机制的认识，更不利于摸清国内铟资源家底。因此，加强对典型伴生铟矿床的详细研究，进而建立更加详细的数据库是亟需开展的重要工作。
Abstract
Indium (In) is an important strategic mineral in short supply in the 21st century, which is of great significance to national stability, development and improvement of international competitiveness. China has the most abundant indium resources in the world, but no independent deposit of indium has been discovered. There are 57 associated indium deposits, which have the potential of cadmium (Cd), gallium (Ga) and germanium (Ge). Based on a detailed review of the regional distribution, genetic types, formation ages, indium-bearing minerals, independent indium minerals and enrichment regularity of 57 associated indium deposits, we summarized the research status and development direction of indium mineralization. The indium-bearing deposits are highly concentrated in the eastern part of the Central Asian Orogenic Belt and South China. There are seven genetic types, including skarn type, magma-hydrothermal type, marine volcanic-rock type, continental volcanic-rock type, superimposed (composite/modified) type, porphyry type, and metamorphosed type. Indium is mainly hosted in sphalerite without exception, and is recycled as by-product. 85% of the indium-bearing deposits were formed in the Mesozoic, with a small number of deposits in the Paleogene and pre-Mesozoic. At present, 19 indium independent minerals have been discovered, only 5 indium independent minerals were found in China. Roquesite (CuInS2) is the most common indium independent mineral that has been found in our country，other indium independent minerals such as natural indium and hydroxindium（InSb）are reported to occur only in specific associated indium deposits. At present, the skarn associated indium deposits, which are located in the southwestern margin of the Yangtze block, get more attention than other deposits. The research of the other six deposit types scattered throughout other areas were studied less. This is a limit not only to understand the indium enrichment mechanism, but also to find out new indium resources. Therefore, it is urgent to strengthen the detailed study of typical associated indium deposits and establish a more detailed database.
