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微量元素和Pb同位素对西藏雅鲁藏布构造带日喀则蛇绿岩形成环境的制约

佘宇伟, 朱祥坤, 何源, 马健雄, 李世珍, 孙剑, 高兆富, 史富强, 唐超

佘宇伟, 朱祥坤, 何源, 马健雄, 李世珍, 孙剑, 高兆富, 史富强, 唐超. 微量元素和Pb同位素对西藏雅鲁藏布构造带日喀则蛇绿岩形成环境的制约[J]. 中国地质, 2020, 47(3): 664-677. DOI: 10.12029/gc20200308
引用本文: 佘宇伟, 朱祥坤, 何源, 马健雄, 李世珍, 孙剑, 高兆富, 史富强, 唐超. 微量元素和Pb同位素对西藏雅鲁藏布构造带日喀则蛇绿岩形成环境的制约[J]. 中国地质, 2020, 47(3): 664-677. DOI: 10.12029/gc20200308
SHE Yuwei, ZHU Xiangkun, HE Yuan, MA Jianxiong, LI Shizhen, SUN Jian, GAO Zhaofu, SHI Fuqiang, TANG Chao. Trace elements and Pb isotope of the mafic rocks from the Xigaze ophiolite of Yarlung Zangbo suture zone, southern Tibet: Constraints on the tectonic setting[J]. GEOLOGY IN CHINA, 2020, 47(3): 664-677. DOI: 10.12029/gc20200308
Citation: SHE Yuwei, ZHU Xiangkun, HE Yuan, MA Jianxiong, LI Shizhen, SUN Jian, GAO Zhaofu, SHI Fuqiang, TANG Chao. Trace elements and Pb isotope of the mafic rocks from the Xigaze ophiolite of Yarlung Zangbo suture zone, southern Tibet: Constraints on the tectonic setting[J]. GEOLOGY IN CHINA, 2020, 47(3): 664-677. DOI: 10.12029/gc20200308

微量元素和Pb同位素对西藏雅鲁藏布构造带日喀则蛇绿岩形成环境的制约

基金项目: 

中国地质调查局项目 121201102000150069

国家自然科学基金项目 41603022

详细信息
    作者简介:

    佘宇伟, 男, 1983年生, 博士后, 矿物学、岩石学、矿床学专业; E-mail:sheyuwei@cags.ac.cn

    通讯作者:

    朱祥坤, 男, 1961年生, 研究员, 地球化学专业; E-mail:xiangkun@cags.ac.cn

  • 中图分类号: P588.12+5;P595

Trace elements and Pb isotope of the mafic rocks from the Xigaze ophiolite of Yarlung Zangbo suture zone, southern Tibet: Constraints on the tectonic setting

Funds: 

China Geological Survey Program 121201102000150069

National Natural Science Foundation of China 41603022

More Information
    Author Bio:

    SHE Yuwei, male, born in 1983, postdoctor researcher, majors in minerlogy, petrogoly and mineral deposit geology; E-mail:sheyuwei@cags.ac.cn

    Corresponding author:

    ZHU Xiangkun, male, born in 1961, senior researcher, majors in geochemistry; E-mail:xiangkun@cags.ac.cn

  • 摘要:

    西藏南部雅鲁藏布构造带分布有一系列蛇绿岩体。人们对这些蛇绿岩体的形成环境仍然存在较大的争议。雅鲁藏布构造带中段日喀则蛇绿岩路曲和大竹曲岩体镁铁质岩石的微量元素和Pb同位素特征指示其母岩浆起源于亏损地幔源区。这些镁铁质岩石的La/Sm和Sm/Yb比值显示其岩浆产生于尖晶石二辉橄榄岩地幔经过大约10%部分熔融作用。综合岩相学和全岩主量元素特征暗示这些镁铁质岩石形成于无水玄武质岩浆。而且这些镁铁质岩石的微量元素和REE元素配分模式均非常相似于N-MORB,除了弱Nb-Ta负异常。这些特征表明路曲和大竹曲岩体形成于大洋中脊环境。此外,路曲和大竹曲镁铁质岩石的Pb同位素结果指示其地幔源区与印度洋MORB地幔域具有相似的地球化学特征。这些镁铁质岩石N-MORB标准化微量元素模式显示弱Nb-Ta负异常可能是由于其地幔源区交代了古老的俯冲带物质。

    Abstract:

    A series of ophiolitic massifs are distributed along the Yarlung Zangbo Suture Zone (YZSZ), southern Tibet. However, the formation settings of these ophiolites are still controversial. Trace elements and Pb isotope geochemical features indicate that the magmas that formed the mafic rocks in the Luqu and Dazhuqu massifs of the Xigaze ophiolite in YZSZ were derived from the depleted mantle source. The La/Sm and Sm/Yb ratios of the mafic rocks show that their parental magmas were produced by ~10% partial melting of spinal lherzolite. Combined with the petrographic observations and major elements of the mafic rocks, the authors hold that they were formed from an anhydrous basaltic magma. Furthermore, the normalized patterns of trace elements and REE of the mafic rocks are very similar to those of N-MORB, except for weakly negative Nb-Ta anomalies. These features indicate that the Luqu and Dazhuqu massifs were formed in the MOR environment. Moreover, the Pb isotope of the mafic rocks indicates that their mantle sources have similar geochemical characteristics to Indian MORB mantle domain. N-MORB normalized trace element patterns of the mafic rocks show that weakly negative Nb-Ta anomalies might have resulted from the process that their mantle source metasomatized old subducted materials.

  • 稀土(Rare earth)是元素周期表中镧系元素和钪、钇共17种金属元素的总称。稀土是重要的自然资源,更是宝贵且关键的战略资源,在民用和军事方面用途十分广泛,同时也是先进装备制造业、新能源、新兴产业等高新技术产业不可或缺的原材料。在全球范围内,稀土资源分布不均,其主要分布于美国、俄罗斯、中国、印度、巴西等国家。中国稀土储量约占世界总储量的23%,却承担了世界90%以上的市场供应(中华人民共和国国务院新闻办公室, 2012)。经半个多世纪的过度开采,中国稀土资源保有储量及保障年限不断下降,鉴于此,发现和利用新类型稀土矿,可有效提高中国稀土资源储量,有力保障国家稀土资源供给安全。

    稀土矿床按成因分类主要有碱性岩—碱性超基性岩型、碳酸岩型、花岗岩型、砂矿型以及风化壳型(徐光宪, 1995);按工业类型分类主要有稀土-磁铁矿矿床、含稀土碳酸岩矿床、花岗岩风化壳型稀土矿床、含稀土伟晶岩矿床、含稀土磷块岩矿床以及独居石砂矿床(矿产资源工业要求手册, 2014)。近年来,多位学者报道在贵州威宁地区二叠系宣威组一段黏土岩中富含稀土元素,但是由于该稀土资源的综合利用技术多年来未取得突破(黄训华, 1997; 张震和戴朝辉, 2010; 周灵洁, 2012),稀土元素的赋存状态、富集机理以及稀土矿床成因类型等方面存在较大争议。2018年以来,笔者在滇东—黔西地区开展地质调查,发现研究区内广泛发育的二叠系宣威组富稀土黏土岩系属沉积成因,有别于Wang et al.(2018)提及的南方离子吸附型稀土矿,而类似于文俊等(2021)报道的川南沐川地区宣威组底部古风化壳-沉积型铌、稀土矿,该新类型稀土矿具有矿石禀赋好、矿层厚度大且较连续、“关键稀土元素(Critical rare earth element; Pr, Nd, Tb, Dy)”占比较高等特点,并伴生有铌、锆、镓等有价元素,其中镓的平均品位高达70.5×10-6,高于工业品位(Zhang et al., 2010)。另外,在稀土资源开发利用方面取得了重大突破,针对该稀土资源研发了“选择性浸出”新工艺(徐璐等, 2020),使稀土回收率可达90%以上,该新类型稀土资源有望实现规模化工业利用。滇东—黔西地区沉积型稀土资源的发现与利用,将有力支撑国家关键稀土资源战略储备。

    滇东—黔西地区大地构造位置位于扬子板块西缘(潘桂棠等, 2009),以北西向康定—水城断裂、北东向弥勒—师宗深大断裂带以及近南北向小江断裂所挟持的三角形地带(图 1)。区内地层属华南地层大区的扬子地层区之上扬子地层分区,主体位于黔西北地层小区,部分涉及到云南的昭通地层小区及曲靖地层小区。晚中生代以前主要是海相碳酸盐岩及陆源硅质碎屑岩,以后则主要为陆相沉积。火成岩主要为海西晚期陆相溢流的峨眉山玄武岩及同源异相的浅成侵入岩。

    图  1  研究区大地构造位置图(据骆耀南, 1985; 张志斌等, 2006
    ①—怒江断裂;②—金沙江—红河断裂;③—鲜水河断裂;④—龙门山山前断裂;⑤—小金河断裂;⑥—箐河—程海断裂;⑦—安宁河—绿汁江断裂;⑧—小江断裂;⑨—康定—水城断裂;⑩—弥勒—师宗断裂
    Figure  1.  Sketch map showing geotectonic position of the research area (after Luo Yaonan, 1985; Zhang Zhibin et al., 2006)
    ①-Nujiang fault; ②-Jinsha River—Red River fault; ③-Xian Shui River fault; ④-Longmen Mountain piedmont fault; ⑤-Xiao Jian River fault; ⑥-Jing River—Chenghai fault; ⑦-Anning River—Lü zhi River fault; ⑧-Xiao River fault; ⑨-Kang ding—Shui cheng fault; ⑩-Mile—Shizong fault

    在研究区内采集了186件宣威组一段沉积型稀土矿石样品,正样经破碎研磨至200目,取缩分样50 g/件,送至中国地质科学院矿产综合利用研究所分析测试中心,利用电感耦合等离子体质谱仪(Perkinelmer Optima Nexion 350X)测得稀土配分数据;再取稀土含量(TREO)较高的毛家坪矿点、鱼布沟矿点缩分样20 g/件,送至中国地质科学院矿产综合利用研究所岩石与工艺矿物学研究室,利用X射线衍射仪(日本理学Ultima Ⅳ)测得主要矿物成分。选取稀土含量(TREO)较高的毛家坪矿点、鱼布沟矿点矿石副样,块样用切割机(MecatomeT330)切成3 cm×1 cm×2 cm样品,用环氧树脂镶嵌制光片坯样;松散样经研磨至40目,用环氧树脂镶嵌制砂片坯样。以上坯样用自动磨抛机(EcomeT300)制得直径为3.5 cm圆柱形待测样品,将待测样品送至中国地质科学院矿产综合利用研究所岩石与工艺矿物学研究室,利用英国蔡司(ZEISS)Sigma 500型场发射扫描电镜及配套的德国布鲁克能谱仪(EDS)获取数据,并应用矿物特征自动定量分析软件(AMICS)进行矿物参数全自动定量分析。

    研究区内富稀土岩系发育于二叠系宣威组一段(P3x1)。宣威组出露面积较广(图 2),北至昭通金阳—大关一带,向南经昭通、威宁一直延伸至宣威—六盘水等地,呈北窄南宽的形态展布。宣威组平行不整合于二叠系峨眉山玄武岩组(P2-3em)之上、整合于三叠系东川组(T1dc)之下,是一套乐平世滨岸及湖沼相与同期曲流河相伴生产出的沉积地层,并且多出现在河泛平原背景上,无独立的大型湖泊沉积体系(戴传固, 2017)。

    图  2  研究区地质简图
    Figure  2.  Sketch Geological map of the study area

    据笔者对威宁县哲觉镇小箐沟(东经103°59′ 08″,北纬26°36′37″)二叠系宣威组一段典型地层剖面(Pm201)研究,查明宣威组一段富稀土岩系主要为灰白色铝土质黏土岩与粉砂质黏土岩互层(图 3a、b),偶见植物碎屑,中部夹砾屑砂岩(图 3f),砾屑呈次圆状,粒度2~4 mm不等,由下往上砾屑粒度表现出粗—细—粗的渐变特征;岩石碎裂呈砂状、松散片状(图 3c),局部可见层理构造;稀土含量较高的岩石主要为铝土质黏土岩(图 3de)、粉砂质黏土岩(⑨~⑪层,⑬~⑮层)。

    图  3  贵州威宁哲觉镇宣威组一段(P3x1)剖面-柱状图
    a—宣威组一段典型剖面;b—宣威组一段柱状图;c、d、e—铝土质黏土岩;f—砾屑砂岩
    Figure  3.  Typical profile and histogram of the first part of Xuanwei Group (P3x1) in the Zhejue town of Weining area, Guizhou Province
    a-Typical section of the first part of Xuanwei Group; b-Histogram of the first passage of Xuanwei Group; c, d, e-Bauxitic clay rock; f-Gravel sandstone

    研究区沉积型稀土矿石主要为深灰—灰白色铝土质黏土岩(图 3cde),具微细粒—隐晶质结构、鳞片状、块状构造。据偏光显微镜、X射线衍射仪、扫描电镜(图 4a)、AMICS矿物分析系统等仪器综合测试分析,结果显示矿石由黏土矿物(高岭石≈83%、埃洛石≈2%、伊利石 < 1%、绿泥石 < 1%)、金属氧化物(锐钛矿≈5%、褐铁矿≈1%、磁铁矿 < 1%、水铝石 < 1%)、硅酸盐矿物(石英+蛋白石 < 4%、火山玻璃≈2%)、金属硫化物(黄铁矿≈0.2%)以及其他方解石、针铁矿等微量矿物组成(徐莺等, 2018)。另外,偶见极少量的氟碳铈矿(图 4b)、方铈矿、磷铝铈矿等独立稀土矿物,其总含量 < 0.1%;以及少量锆石、磷灰石、金红石等含稀土元素的非独立稀土矿物,其总含量 < 1%。

    图  4  稀土矿石扫描电镜照片
    a—扫描电镜照片;b—独立稀土矿物显微照片;Q—石英;Kl—高岭石;Lm—褐铁矿;Bsn—氟碳铈矿
    Figure  4.  Scanning electron microscope photograph of rare earth ores
    a-Scanning electron microscope photograph; b-Micrograph of independent rare earth minerals; Q-Quartz; Kl-Kaolinite; Lm-Limonite; BsnBastnaesite

    本文作者在研究区内优选二叠系宣威组(P3x)出露较好的区域,通过32个探槽工程、6个剥土工程地表控制及22个钻探工程深部验证,初步查明研究区二叠系宣威组(P3x)一段稀土矿层厚度2~18 m不等,单个矿石样品TREO含量最高为1.6%,圈定三处稀土矿找矿靶区(图 5):

    图  5  稀土矿找矿靶区分布图
    1—稀土矿体;2—断层;3—找矿靶区及其编号
    Figure  5.  Sketch map showing distribution of the target areas for rare earth ore
    1-Rare earth deposit; 2-Fault; 3-Target area for prospecting and its number

    (1)Ⅰ号找矿靶区:该靶区矿体形态呈层状、似层状,圈定一个矿体,矿体倾角26°~31°,矿体厚度2.96~18.92 m,矿体在地表出露较连续,沿走向延伸可达8 km,矿体TREO加权平均品位为0.21%(边界品位:0.18%,下同),该找矿靶区内推断资源量约4万t,矿床规模达小型。

    (2)Ⅱ号矿找矿靶区:该靶区矿体形态呈层状、似层状,共圈定出上下两个矿层、三个矿体,矿体倾角12° ~17°,矿体TREO加权平均品位0.23% ~ 0.39%,矿体厚度5.85~9.23 m,其中主矿体沿倾向延伸可达1.6 km,该找矿靶区内推断资源量约25万t,矿床规模达中型,并具有达大型的潜力。

    (3)Ⅲ号找矿靶区:该靶区矿体形态呈层状、似层状,共圈定出上下两个矿层、十个矿体,矿体倾角4° ~10°不等,矿体TREO加权平均品位0.18% ~ 0.46%,矿体厚度1.29~2.99 m。其中主矿体在地表出露连续,深部钻探控制也较稳定,沿倾向延伸可达2 km,该找矿靶区内推断资源量约2万t,矿床规模为小型。

    综上所述,该区稀土资源规模大,矿体埋藏浅,产状较缓且连续,有利于大规模露天开采。

    笔者在研究区内、找矿靶区以外的昭通、鲁甸、威宁炉山—东风—二塘、六盘水大湾、宣威大井等地(图 2),采集了宣威组一段铝土质黏土岩样品,分析结果显示均有稀土矿化异常,十余处稀土TREO品位超0.1%,最高品位0.42%,算数平均品位0.2%,矿体出露厚度2~6 m不等,推测滇东—黔西地区沉积型稀土资源找矿潜力巨大,远景资源量超100万t。

    物源区岩石经风化剥蚀形成的碎屑物质再搬运至沉积区沉积成岩,通常沉积岩继承了物源区岩石的稀土配分特征,风化和成岩作用对沉积岩中稀土元素再分配影响不大(Mclennan, 1993),所以稀土可作为一种有效的示踪物质。

    在研究区内优选4条宣威组典型剖面(Pm101、Pm104、Pm205、Pm207),逐层采集岩石样品,分别按玄武岩、铁质黏土岩、铝土质黏土岩、黏土质粉砂岩、炭质黏土岩和砾岩进行稀土元素球粒陨石标准化,从稀土配分模式(图 6)可以看出宣威组富稀土岩系中所有样品均与峨眉山玄武岩均具有相对富集轻稀土元素、亏损重稀土元素、呈现右倾模式的特征;不同的是,大部分铁质黏土岩、黏土质粉砂岩与玄武岩具有更加相近的配分模式,即都只表现出轻微的负Eu异常;而铝土质黏土岩层作为主要的含矿层却表现为明显的负Eu异常(田恩源等, 2020)。

    图  6  全岩球粒陨石稀土配分图(据田恩源等, 2020修改;标准化数值据Sun and McDonough, 1989)
    1—玄武岩;2—铁质粉砂质黏土岩;3—铝土质黏土岩;4—炭质粘土岩;5—黏土质粉砂岩;6—砂质砾岩
    Figure  6.  Chondrite-normalized REE patterns of the samples (modifiled from Tian Enyuan et al., 2020; standardized values modifiled from Sun and McDonough, 1989)
    1-Basalt; 2-Fe-Silty clay rock; 3-Bauxitic clay rock; 4-Carbonaceous clay rock; 5-Clayey siltstone; 6-Sandy conglomerate

    滇东—黔西地区沉积型稀土矿石中关键稀土元素(CREO)高于国内正在开发利用的四川冕宁碳酸岩型、白云鄂博碳酸岩型、山东微山碳酸岩型以及部分南方离子吸附型等大型、超大型稀土矿床,同样也高于国外即将开发利用的美国芒廷帕斯碳酸岩型、格陵兰岛碱性岩型等超大型稀土矿床。另外,该沉积型稀土资源与离子吸附型、古砂矿型稀土矿对比,在矿石品位、资源规模、集中程度、开采方式、环境影响等方面具有较大的优势,其开发前景巨大(图 7ab)。

    图  7  世界典型稀土矿床“关键稀土元素(CREE)”含量对比图(矿床序号如表 1所示)
    a—关键稀土元素含量-资源量对比图;b—关键稀土元素含量-矿石品位对比图
    Figure  7.  CREE content comparison diagram of typical rare earth deposits in the world (the sequence number of deposits is shown in Table 1)
    a-CREO-Resource comparison diagram; b-CREO-ore content comparison diagram
    表  1  世界典型稀土矿床对比表
    Table  1.  Comparison table of typical rare earth deposits in the world
    下载: 导出CSV 
    | 显示表格

    笔者开展该沉积型稀土矿原矿铵盐浸出对比实验,结果表明稀土原矿中仅有少量(< 5%)稀土元素以离子吸附状态赋存于矿石中。通过多轮技术攻关,利用选择性浸出技术控制焙烧温度和焙烧时间,准确破坏稀土矿中高岭石的特定结构,脱去其层状结构中的羟基,变为高活性的偏高岭石,但偏高岭石仍保持了片状的结构特征。焙烧温度低于550℃,高岭石未转化为偏高岭石,稀土无法有效浸出,焙烧温度高于850℃,高岭石结构被完全破坏,硅和铝晶型会发生变化,对稀土元素进行重新包裹,导致稀土元素无法有效浸出,焙烧过程中不使用添加剂避免产生额外的有害废气。该技术通过协同控制焙烧和浸出条件,选择性浸出偏高岭石中的稀土元素,稀土元素浸出率高于90%,同时主要杂质铝、铁、钛和硅浸出率均<5%,有效抑制杂质大量进入富稀土料液。该技术申请了国家发明专利(徐璐等, 2020)。该技术的推广应用,有望使研究区内的稀土资源实现规模化工业利用。

    滇东—黔西地区稀土矿的成因研究程度不高,且存在较大争议,目前主要有三种观点:一是风化淋滤型,杨瑞东等(2006)王伟(2008)以及Yang et al.(2008)通过分析稀土含矿层的地球化学特征,认为该矿床属与峨眉山玄武岩有关的风化壳型,峨眉山玄武岩及凝灰岩被强烈风化淋漓形成高岭石黏土岩,母岩中辉石的稀土元素被解析出来,被高岭石颗粒吸附,使稀土富集,形成稀土矿床;葛枝华(2018)同样赞同风化淋滤型稀土的观点,认为玄武岩风化过程实质就是一种脱硅富铝的过程,辉石、长石类矿物强烈分解,铁铝钛等氧化物明显增加,Ca、Na、Mg、K强烈迅速淋失,SiO2的含量不断降低,元素的迁移活动顺序是CaO>MgO>Na2O>SiO2,认为稀土元素通过风化淋滤作用在风化壳中不断富集起来。二是沉积-改造型,张海(2014)认为稀土矿床的形成与母岩的风化作用、沉积成岩作用以及地下流体作用有关,是沉积-再造型稀土矿床;黄训华(1997)周灵洁(2012)张海(2014)吴承泉等(2019)通过稀土物源、地球化学特征分析,认为稀土矿物源不仅是峨眉山玄武岩,还应包括后期喷发的中酸性火成岩,经风化剥蚀后形成富集稀土的玄武岩质、凝灰质及少量长英质碎屑,经水介质搬运至沉积盆地形成高岭石硬质黏土岩,成岩过程中遭受一定程度的热液蚀变,促进稀土元素再富集;三是部分学者通过对比研究二叠纪峨眉山玄武岩及其同期长英质凝灰岩的地球化学特征,认为稀土异常富集与峨眉山玄武岩同期的碱性岩浆活动产生的凝灰岩有关,并接受了后期低温热液改造(Xu et al., 2001; Zhou et al., 2002; Long et al., 2004; Dai et al., 2010; Zhao et al., 2016)。

    笔者研究发现,区域上宣威组富稀土岩系整体呈层状产出,从滇东到黔西横向演化和相变特征清晰;富稀土岩系底部常见河道相砾岩,辫状河沉积体系发育,层内偶见植物碎屑化石,层间发育水平层理等典型沉积构造;稀土含量较高的岩石主要为灰白色铝土质黏土岩,矿物组成主要为高岭石以及少量来自玄武岩及凝灰岩的典型矿物;由稀土配分模式看出铁质黏土岩和黏土质粉砂岩与玄武岩相比具有继承性,而铝土质黏土岩呈现出有别于玄武岩的明显负Eu异常特征(田恩源等, 2020);滇东—黔西地区位于上扬子陆块西缘,晚震旦世以来,长期处于相对稳定的台地沉积环境,区内无岩浆活动,不具备热液型稀土及南方离子吸附型稀土的成矿条件。基于以上认识,本文认为峨眉山玄武岩及同期的凝灰岩为富稀土岩系提供了主要的物质来源,而富稀土岩系中铝土质黏土岩很可能在沉积成岩过程中混入了大量上地壳富稀土物源区的物质,使得铝土质黏土岩中稀土异常富集。综上所述,本文认为滇东—黔西地区稀土资源成因类型为沉积型,是一种新类型的稀土资源。

    该稀土矿中稀土元素的赋存状态存在较大争议,前人分析矿石中稀土元素含量的高低可能与矿物组分有密切关系(周灵洁, 2012; Zhou et al., 2013; Zhang et al., 2016; Zhao et al., 2016, 2017; He et al., 2018)。在风化过程中,如果含稀土元素的副矿物抗风化能力弱,稀土元素则容易从副矿物中释放出来,以离子形式迁移富集于黏土矿物中,黏土矿物含量越高,稀土含量往往也相应比较高,稀土含量与黏土矿物含量就有较高的正相关性,据此推测认为稀土元素极有可能以离子吸附相和富含稀土元素的残余独立矿物相组成,与高岭石等黏土矿物含量密切相关;徐莺等(2018)利用电子探针、X射线衍射等现代分析测试手段并结合矿石选冶试验,认为稀土元素以类质同象为主、离子吸附相为辅的形式赋存于高岭石质黏土岩中;黄训华(1997)吴承泉等(2019)通过分析在强烈风化条件下母岩被解析形成的稀土元素可能存在的赋存状态,认为稀土元素可能以离子吸附态、胶体吸附态等的混合态赋存于高岭石硬质黏土岩中。以上研究并未提供确凿证据证明稀土元素赋存状态。本文作者开展多组原矿铵盐浸出对比实验,稀土元素浸出率不超过20%,间接说明了稀土原矿中以离子吸附态赋存的稀土元素占比很低;据矿石岩矿鉴定,查明以独立稀土矿物形式赋存的稀土元素占比<0.1%,以类质同像(非独立稀土矿物)形式赋存的稀土元素占比也很低;而通过550℃~850℃焙烧选择性浸出技术,准确破坏稀土元素载体矿物——高岭石的特定结构,稀土元素浸出率高于90%。基于以上研究,推测稀土元素极有可能以某种形态赋存于高岭石矿物晶体层间间隙中。

    随着全球新材料、新技术、新能源、高新电子、高端装备制造、先进军事装备等战略性产业迅猛发展,加快了对原材料的结构性调整,一批新兴战略性关键矿产成为各国竞相争夺的资源。根据稀土各元素特有的性质,轻稀土中的Pr、Nd,重稀土中的Tb、Dy等元素由于其在高强度永磁行业、新能源汽车产业、高端声光电材料等方面具备不可替代的地位,这些制约着全球新兴产业、高新科技健康发展的稀土元素称之为“关键稀土元素(CREE)”。据上海有色网公布的2020年6月稀土氧化物实时交易均价(据上海有色网未公布Tm2O3、Yb2O3、Lu2O3成交均价)显示(图 8),Pr、Nd、Tb、Dy关键稀土氧化物价格分别29.5万元/t、28.0万元/t、419万元/t、194万元/t,合计约占所有单一稀土氧化物价格总和的88%,可见关键稀土元素具有极高的经济价值和重要的战略地位。

    图  8  稀土氧化物价格对比柱状图
    Figure  8.  Price comparison bar chart of rare earth oxide

    滇东—黔西地区发现的沉积型稀土矿具有矿层厚、矿石品位高、资源潜力大、矿石中关键稀土元素(CREE)占比高等特点,特别是矿石选冶新工艺取得重大突破,使该类型稀土矿可能实现规模化工业利用。该沉积型稀土矿的发现既丰富了全球稀土资源工业类型,又支撑了国家关键稀土资源战略储备。

    (1)滇东—黔西地区发育于二叠系宣威组的稀土矿,其成因类型属沉积型。

    (2)稀土元素极有可能以某种形式赋存于高岭石矿物晶体层间间隙中。

    (3)该沉积型稀土矿具有矿体厚度大、矿石品位高、资源潜力大、开采成本低、矿石中关键稀土元素(CREO)占比高等优点,其开发利用前景较好。

    (4)该沉积型稀土资源的发现既丰富了全球稀土资源工业类型,又支撑了国家关键稀土资源战略储备。

    致谢: 全岩微量元素测试得到了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胡静老师的帮助,在此表示感谢。
  • 图  1   雅鲁藏布构造带及蛇绿岩简图

    a—雅鲁藏布蛇绿岩分布及镁铁质岩石锆石U-Pb年龄(修改自An et al., 2014吴福元等, 2014);b—日喀则蛇绿岩分布及这次研究的采样点位置(修改自王希斌等,1987

    Figure  1.   Simplified geological map of Yarlung -Zangbo suture zone and ophiolitic massifs

    a-Distribution of the Yarlung Zangbo ophiolites and their zircon U-Pb ages from mafic rocks (modified from An et al., 2014; Wu Fuyuan et al., 2014); b-Distribution of the Xigaze ophiolitic massifs and sampling locations of this study (modified from Wang Xibin et al., 1987)

    图  2   日喀则蛇绿岩野外照片

    a—路曲岩体蛇绿混杂岩;b—路曲岩体辉绿岩脉侵入地幔橄榄岩(蛇纹岩);c—大竹曲岩体层状辉长岩;d—大竹曲岩体块状辉长岩和辉绿岩;e—大竹曲岩体含斜长石斑晶的辉绿岩;f—路曲岩体枕状玄武岩

    Figure  2.   Field photos of the Xigaze ophiolite

    a-Ophiolitic mélange of the Luqu massif; b-Diabase dike that intruded into mantle peridotite (serpentinite) of the Luqu massif; c-Layered gabbro of the Dazhuqu massif; d-Massive gabbro and diabase of the Dazhuqu massif; e-Plagioclase phenocrysts in diabase of the Dazhuqu massif; f-Pillow basalts of the Luqu massif

    图  3   日喀则蛇绿岩镁铁质岩石显微照片

    a—辉长岩中半自形单斜辉石和自形-半自形斜长石构成辉长结构;b—辉长岩中粗粒单斜辉石中包裹自形—半自形的斜长石晶体;c—辉绿岩中细粒辉石和自形斜长石组成典型的辉绿结构;d—辉绿岩中自形斜长石斑晶;e—玄武岩中自形斜长石和他形单斜辉石;f—玄武岩中自形斜长石和他形单斜辉石斑晶

    Figure  3.   Petrographic microphotos of the mafic rocks from the Xigaze ophiolite

    a-Gabbro texture consisting of subhedral clinopyroxene and subhedral to euhedral plagioclase in gabbro; b-Subhedral-euhedral plagioclase enclosed by coarse-grain clinopyroxene in gabbro; c-Diabasic texture consisting of fine grained clinopyroxene and euhedral plagioclase in diabase; d-Euhedral plagioclase phenocrysts in diabase; e-Fine grained plagioclase and clinopyroxene in basalt; f-Euhedral plagioclase and anhedral clinopyroxene phenocrysts in basalt

    图  4   日喀则蛇绿岩路曲和大竹曲镁铁质岩石全岩TAS图解

    Figure  4.   Diagram of TAS for whole rock composition of the mafic rocks of the Luqu and Dazhuqu massifs from the Xigaze ophiolite

    图  5   日喀则蛇绿岩路曲和大竹曲岩石球粒陨石标准化REE配分模式(a,c)及N-MORB标准化微量元素配分模式(b,d)

    (球粒陨石和N-MORB标准化值据Sun and McDonough, 1989; 用于对比的OIB、E-MORB、N-MORB数值据Sun and McDonough, 1989

    Figure  5.   Chlondrite-normalized REE patterns (a, c) and N-MORB normalized trace elements patterns (b, d)of Xigaze ophiolite

    Normalized values, and N-MORB, OIB, E-MORB values after Sun and McDonough (1989)

    图  6   全岩Pb同位素比值图解

    a-(208Pb/204Pb)t-(206Pb/204Pb)t; b-(207Pb/204Pb)t-(206Pb/204Pb)t;矫正年龄为t=140 Ma。太平洋和北大西洋MORB和印度洋MORB范围据Mahoney et al.1998Zhang et al. 2005。现代大洋沉积物(GLOSS, 据Ben Othman et al., 1989, 北半球参考线(NHRL)据Hart, 1984。用于对比的雅鲁藏布蛇绿岩的Pb同位素数据源自文献(牛晓露等, 2006; 钟立峰等, 2006; 徐德明等, 2007; 刘飞等, 2013; Liu et al., 2015

    Figure  6.   Plots of Pb isotope ratios

    a-(208Pb/204Pb)tversus (206Pb/204Pb)t; b-(207Pb/204Pb)t versus (206Pb/204Pb)t at 140 Ma. Fields of Pacific and North Atlantic MORB, and India MORB after Mahoney et al. (1998) and Zhang et al. (2005). Field of GLOSS after Ben Othman et al., 1898 and NHRL after Hart (1984). The data of Pb isotope of the Yarlung-Zangbo ophiolite after Niu et al. (2006), Zhong et al. (2006), Xu et al. (2007), Liu et al.(2013, 2015)

    图  7   全岩La/Sm-Sm/Yb图解(据Aldanmaz et al., 2000

    PM、N-MORB、E-MORB数据源自Sun and McDonough (1989)

    Figure  7.   Diagram of La/Sm versus Sm/Yb (after Aldanmaz et al., 2000)

    PM, N-MORB, E-MORB data after Sun and McDonough (1989)

    图  8   微量元素构造环境判别图

    a-Zr/Y-Zr(据Pearce, 2000);b-Nb/Yb-Th/Yb(据Pearce, 2008);c-Nb/Th-Th/La(据Godard et al., 2006);弧后盆地、洋中脊扩张中心、弧前玄武岩数据源自于PETDB数据库(http://www.petdb.org

    Figure  8.   Discriminant diagrams of tectonic setting

    a-Zr/Y versus Zr (after Pearce, 2000), b-Nb/Yb versus Th/Yb(after Pearce, 2008); c-Nb/Th versus Th/La(after Godard et al., 2006). The data of back-arc basalt, mid-oceanic ridge basalt, fore-arc basalt after PETDB database

    表  1   日喀则蛇绿岩路曲和大竹曲岩体镁铁质岩石全岩主量元素(%)和微量元素(10-6)成分

    Table  1   The compositions of whole-rock major (%) and trace (10-6) elements of the mafic rocks from the Luqu and Dazhuqu massifs of the Xigaze ophiolite

    下载: 导出CSV

    表  2   日喀则蛇绿岩路曲和大竹曲镁铁质岩石Pb同位素成分

    Table  2   The compositions of Pb isotope of mafic rocks from the Luqu and Dazhuqu massifs of the Xigaze ophiolite

    下载: 导出CSV
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  • 收稿日期:  2018-07-15
  • 修回日期:  2019-12-14
  • 网络出版日期:  2023-09-25
  • 刊出日期:  2020-06-24

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