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阿尔泰青河伟晶岩中电气石成分和硼同位素对伟晶岩
*
体系演化及其与围岩相互作用的示踪
1,
2 *
1* 1
郑贝琪 陈斌 孙杨
ZHENG BeiQi1,2 ,CHEN Bin1** and SUN Yang1
1. 南方科技大学地球与空间科学系,深圳 518055
2. 韶关学院旅游与地理学院,韶关 512005
1. Department of Earth and Space Sciences,Southern University of Science and Technology,Shenzhen 518055,China
2. School of Tourism and Geography,Shaoguan University,Shaoguan 512005,China
2022-06-29 收稿,2022-09-26 改回 .
Zheng BQ,Chen B and Sun Y. 2023. Tracing the evolution of the pegmatite system and its interaction with the country
rocks by chemical and boron isotope compositions of tourmaline in the Qinghe pegmatite from the Chinese Altay orogen. Acta
Petrologica Sinica,39( 1) : 187 - 204,doi: 10. 18654 /1000-0569 /2023. 01. 13
Abstract Tourmaline crystalized in pegmatites and its surrounding altered wallrocks record the evolution,fluid exsolution and fluid-
rock interactions of the pegmatite system. We conducted systematic elemental and boron isotope studies on tourmalines from a pegmatite
dyke and its surrounding country rocks in Qinghe ( the Altay orogeny) to investigate the origin and evolution of the pegmatite-forming
magma and the scale of its fluid exsolution. The pegmatite dyke can be divided into the border,the intermediate and the core zones
according to its textures and mineralogy assembalge. Outwards from the contact,banded altered rocks,fine-grained altered rocks to
coarse-grained altered rocks appear in sequence. The B and P in the pegmatite-derived fluids,together with Fe and Mg in the country
rocks,provided necessary sources for the formation of the tourmaline. All tourmalines belong to the alkali group,which can be further
classified into schorl to dravite solid-solution series according to the analytical results. Most tourmalines follow the exchange vectors of
( R1 + Al) ( Na + R2) - 1 ,( Al + O) ( R + OH) - 1 ,( Na + Mg) ( Al + X vac ) - 1 ,( X vac Al) ( NaR2 + ) - 1 ,FeMg - 1 and MnMg - 1 ,which
highlight the evolution trends of the increase of the Fe,Mn and Al contents and the decrease of the Na,Mg and Ca contents. Combined
with the content of V and the correlation between Fe3 + and Al,we believe that the primary pegmatite magma was characterized by low
oxygen fugacity,and that the high oxygen fugacity at the edge of the pegmatite dike could be related to the interaction between the
pegmatite-forming magma and the surrounding rocks. In addition,tourmaline from pegmatite has much lower ∑REE and ( La / Yb) N
than that from the granite,which suggests that the pegmatite was not a product after extreme fractionation of a parental granite. Instead,
it originated from the direct melting of mica schist under amphibolite-faces conditions. The slight difference of boron isotope
compositions between the altered and the unaltered wallrocks manifests a limited scale of fluid exsolution from the late-stage barren
pegmatite. Tourmalines from the Qinghe pegmatite exhibit significantly lower δ11 B values than tourmalines from the mica schist,
implying that the mica schist was not the only source for the Qinghe pegmatite,and instead,there might be a certain amount of
claystones.
Key words Pegmatite; Tourmaline; Boron isotope; Altay orogenic belt
摘 要 伟晶岩及其围岩蚀变带的电气石记录了伟晶岩体系的演化、流体出溶以及流体-围岩相互作用的过程。本文对阿
尔泰造山带青河伟晶岩及蚀变围岩中电气石进行了系统的化学成分和硼同位素分析,以探讨伟晶岩体系的源区性质、岩浆演
化、流体出溶规模等重要科学问题。根据矿物成分和结构构造不同,伟晶岩可分为边缘带、过渡带和核部带。蚀变围岩从接
触带开始向外,依次出现带状蚀变围岩、细粒蚀变围岩和粗粒蚀变围岩。伟晶岩蚀变围岩电气石的形成与伟晶岩出溶流体
图2 青河伟晶岩与蚀变围岩产状及对应手标本照片
( a) 伟晶岩与蚀变围岩接触关系及( b) 蚀变围岩分带示意图; 伟晶岩边缘带( c) 、过渡带( d) 和核部带( e) ; 伟晶岩与围岩接触带中带状蚀变
围岩( f) 、细粒蚀变围岩( g) 和粗粒蚀变围岩( h) . Pl-斜长石; Kfs-钾长石; Qtz-石英; Tur-电气石; Ms-白云母; Bt-黑云母
Fig. 2 Occurences and hand specimen photographs of Qinghe pegmatite and altered wallrocks
( a) photograph and( b) simplified sketch of the pegmatite and altered wallrocks; the border zone( c) ; intermediate zone( d) ; core zone ( e) of the
pegmatite dyke; andbanded altered rock( f) ,fine-grained altered rock( g) and coarse-grained altered rock( h) in contect belt of pegmatite and altered
wall rock. Pl-plagioclase; Kfs-K-feldspar; Qtz-quartz; Tur-tourmaline; Ms-muscovite; Bt-biotite
3. 1 伟晶岩中电气石特征
边缘带电气石 半自形-自形,具特征的核-边结构,核部 4 分析方法
浅黄-黄绿色,边部浅绿-深墨绿色,大部分电气石与石英直接 4. 1 电气石主量元素测试
接触,少数电气石边缘生长白云母或斜长石( 图 3a) 。
4. 1. 1 电子探针微区原位主量元素测试
过渡带电气石 半自形-自形,发育环带结构,单偏光下
电子探针成分分析在中国地质大学( 武汉) 配备有 4 道
核部为蓝色-深蓝色,向外变为黄褐色-深黄褐色,粒径 5 ~
波谱仪的 JEOL JXA-8100 电子探针下完成,详细的分析测试
15mm。主要与斜长石共生,细粒白云母充填在斜长石与电 流程见 文 献 ( Yang et al. ,2022 ) 。工 作 条 件 为: 加 速 电 压
气石晶粒间( 图 3b) 。 15kV,加速电流 20nA,束斑直径 10μm。所有测试数据均进
核部带电气石 半自形-自形,发育较复杂环带结构,单 行了 ZAF 校正处理,分析准确度为 1% ~ 5% 。Na、Mg、Al、
偏光下核部为淡蓝色-深蓝色,幔部和边部为黄-黄绿色,粒径 Si、K、Ca、Fe、F 元素特征峰的测量时间为 10s,Ti 和 Mn 元素
> 15mm,主要与斜长石共生,少数斜长石和白云母充填在电 特征峰的测量时间为 20s,上下背景的测量时间分别是峰测
气石晶粒间( 图 3c) 。 量时间的一半。所使用的标样如下: 微斜长石( K) 、镁铝榴
郑贝琪等: 阿尔泰青河伟晶岩中电气石成分和硼同位素对伟晶岩体系演化及其与围岩相互作用的示踪 193
图4 青河伟晶岩和蚀变围岩中电气石分类图解
( a) 基于 X 位占位分类图解( Henry et al. ,
2011) ; ( b) 根据 Mg / ( Mg + Fe) -Na / ( Na + Ca) 对碱性电气石族分类; ( c) 根据 Mg / ( Mg + Fe) -X vac /
( Na + X vac ) 对碱性电气石族分类
Fig. 4 Classification diagrams for tourmalines based on X-site occupancy( a,Henry et al. ,
2011) ,Mg / ( Mg + Fe) vs. Na / ( Na +
Ca) ( b) and Mg / ( Mg + Fe) vs. X vac / ( Na + X vac ) ( c) from the Qinghe pegmatite dyke and altered wallrocks
图5 青河伟晶岩和蚀变围岩中电气石主量元素图解
( a) CaO-K2 O; ( b) Na2 O-K2 O; ( c) Mg-Fe; ( d) Mg-Mn
Fig. 5 Plots for major elements of tourmalines from the Qinghe pegmatite dyke and altered wallrocks
图6 青河伟晶岩和蚀变围岩中电气石的元素替代关系
Fig. 6 Characteristics of compositions of tourmalines from the Qinghe pegmatite dyke and altered wallrocks
图7 青河伟晶岩和蚀变围岩电气石微量元素成分特征
图( e) 用以区分岩浆成因和变质成因电气石( 据 Harlaux et al. ,2020)
Fig. 7 Characteristics of trace elements of tourmalines from the Qinghe pegmatite and altered wallrocks
Discrimination of magmatic and metamorphic tourmaline in Fig. 7e( after Harlaux et al. ,
2020)
图8 青河伟晶岩及各类蚀变围岩电气石硼同位素组成
Fig. 8 Histograms of boron isotope compositions of tourmalines from the Qinghe pegmatite and altered wallrocks
图9 青河伟晶岩及蚀变围岩电气石电子探针分析结果
( a) 伟晶岩边缘带环带电气石 BSE 图像及其区域 Fe 元素( b) 和 Mg 元素( c) 成分分布; ( d) 一颗环带发育良好的边缘带电气石边-核 Mg 元
素含量及 Mg 指数分布; ( e) 带状蚀变围岩电气石 BSE 图像及其区域 Ca 元素( f) 成和 F 元素( g) 成分分布
Fig. 9 EPMA analysis of tourmaline from the Qinghe pegmatite and altered wallrocks
( a) BSE image of tourmaline from the border zone of pegmatite and its mapping of Fe distribution( b) and mapping of Mg distribution ( c) ; ( d) Mg and
Mg # trend in a sector zoning tourmaline; ( e) BSE image of tourmaline from the banded altered rocks and its mapping of Ca distribution ( f) and
mapping of F distribution ( g)
Costa et al. ,
2021) 。伟晶岩核部带和过渡带电气石的 Fe-Al 明围岩中氧逸度较高。这与电气石 Fe
3+
/ Fe2 + 记录的氧逸度
呈正相关,而边缘带电气石 Fe-Al 则为负相关。此外,围岩中 信息一致。我们认为这种较高氧逸度是围岩的固有特征,与
的带状蚀变围岩、细粒蚀变围岩和粗粒蚀变围岩电气石也具 伟晶岩流体交代无关,因为在未蚀变围岩中的电气石同样具
有 Fe-Al 负相关特征。电气石 Fe-Al 负相关关系通常由其 -6 -6
有较高的 V 含量( V = 265 × 10 ~ 366 × 10 ; Zheng et al. ,
3+ 3+ 3+
Fe 和 Al 的替代引起,表明这些电气石比较富集 Fe ,是 2022) 。所以,伟晶岩核部和过渡带的低氧逸度可能代表原
较高氧逸度的体现,而 Fe-Al 正相关则与介质氧逸度较低有 始伟晶岩浆的特征,而伟晶岩脉边缘带的较高氧逸度可能与
3+
关。前人已发表的数据也都表明电气石的 Fe / Fe2 + 可反映
伟晶岩浆与围岩相互作用有关。这与青河伟晶岩矿田其他
介质 氧 逸 度 的 变 化 ( Fuchs et al. ,1998; Watenphul et al. , -6
伟晶岩脉中 电 气 石 的 低 V 含 量 ( 0 ~ 9. 92 × 10 ; Zheng et
3+ 2+
2016) ,即高 Fe / Fe 指示高氧逸度。因此,伟晶岩边缘带
al. ,
2022) 相一致,也与全球造山带中大多数 S 型花岗岩电
和蚀变围岩中电气石 Fe-Al 的负相关特征,都指示其介质氧
气石的 V 含量特征吻合( Sun et al. ,2018; dos Santos Dias et
逸度较高,而伟晶岩核部和过渡带电气石的 Fe-Al 正相关则
al. ,
2019; Nguyen et al. ,
2019) 。
可能表明其氧逸度较低。该推论得到电气石中微量元素特
征的支持,具体如下:
6. 3 电气石对伟晶岩源区性质的指示意义
电气石的微量元素被证实可以示踪介质微量元素组成
( Duchoslav et al. ,
2017; Zhao et al. ,
2021a,b) 。由于 V 是变 6. 3. 1 电气石主微量元素对源区的限制
3+ 4+
价元素,在伟晶岩岩浆不同的氧逸度环境中以 V 、V 和 Kontak et al. ( 2002) 通过对比起源于花岗岩分离结晶和
V 5+
等形式存在( Li and Lee,2004; Lee et al. ,2005) ,而电气 变质沉积岩直接熔融形成的伟晶岩电气石样品后发现,后者
石晶格更偏好 V
5+
( Marlks et al. ,2013) ,因此电气石的 V 含 往往具有更低 REE 总量和( La / Yb) N 比值: 起源于花岗岩分
-6 -6
量可以反演体系氧逸度的变化。从图 7a 和图 10d 可见,伟 离结晶的电气石 REE 总量为 70 × 10 ~ 150 × 10 ,( La /
-6
晶岩核部带电气石( 平均 V = 21. 4 × 10 ) 和过渡带电气石 Yb) N 为 350 ~ 420; 而起源于变质沉积岩直接熔融的伟晶岩
( 平均 V = 49. 7 × 10 - 6 ) 的 V 含量较低,而边缘带电气石 V 含 -6 -6
中电气石的 REE 总量为 3 × 10 ~ 4 × 10 ,( La / Yb) N 为
-6
量较高( 平均 V = 144. 9 × 10 ) ,反映伟晶岩边缘带氧逸度 1. 2 ~ 1. 8。造成这一差别的原因可能与岩浆形成温度不同
显著高于核部带和过渡带。蚀变围岩的电气石都具有高 V 有关。Ayres and Harris( 1997) 根据喜马拉雅结晶片岩的部
-6
含量 ( 带 状 蚀 变 围 岩 V Ave. = 117. 3 × 10 ,细 粒 蚀 变 围 岩 分熔融模拟计算表明,喜马拉雅山淡色花岗岩的稀土元素
V Ave. = 311. 4 × 10 - 6 ,粗粒蚀变围岩 V Ave. = 262. 6 × 10 - 6 ) ,表 ( REE) 不是由贫 REE 的主要反应物 ( 如长石、石英和云母
郑贝琪等: 阿尔泰青河伟晶岩中电气石成分和硼同位素对伟晶岩体系演化及其与围岩相互作用的示踪 199
图 10 青河伟晶岩及蚀变围岩电气石代表性主微量元素图解
( a) 青河伟晶岩电气石与其它造山带花岗岩电气石的∑REE-( La / Yb) N 2008; Shabani et al. ,
对比图( 数据来源: 黄小勇等, 2013; Yang et al. ,
2015; Zhao et al. ,
2019,2021a,c; Duan et al. ,
2020; Han et al. , 2021; Zhang et al. ,
2020; 吴明锴等,
2020; Hu and Jiang, 2021a) ; 青河伟晶岩电
气石与蚀变围岩中电气石∑REE-Mg / ( Mg + Fe) ( b) 、Mg / ( Mg + Fe) -Li( c) 、Mg / ( Mg + Fe-V) ( d) 、MgO-Zn( e) 及 Mg / ( Mg + Fe) -( La / Yb) N
( f) 对比图
Fig. 10 Representative major and trace element relationships of tourmaline from the Qinghe pegmatite and altered wallrocks
( a) plot of ∑REE vs. ( La / Yb) N for tourmalines from the Qinghe pegmatite and granites of other orogenic belts ( data sources: Huang et al. ,
2008;
Shabani et al. , 2013; Yang et al. , 2015; Zhao et al. ,2019,2021a,c; Duan et al. , 2020; Han et al. ,2020; Hu and Jiang,2020; Wu et al. ,2021;
Zhang et al. ,2021a) ; plots of ∑REE and Mg / ( Mg + Fe) ( b) ,Mg / ( Mg + Fe) vs. Li( c) ,Mg / ( Mg + Fe) vs. V( d) ,MgO vs. Zn( e) and Mg / ( Mg
+ Fe) vs. ( La / Yb) N ( f) for tourmalines from the Qinghe pegmatite and altered metapelitic rocks
成,而与花岗岩体系的分离结晶( London,
2018) 无关。 分离结晶的结果,而应该是变质沉积岩直接部分熔融形成的
6. 3. 2 电气石硼同位素对流体出溶规模和伟晶岩源区性质 熔体。变质泥 质 岩 部 分 熔 融 实 验 研 究 表 明 ( White et al. ,
的限制 2007) ,伟晶岩熔体主要是在角闪岩相条件下通过白云母脱
从图 8 可见,本文研究的伟晶岩脉的核部和过渡带电气 水熔融而成。如果不考虑部分熔融过程中硼同位素的分馏,
11
石硼同位素组成基本相同( δ B = - 15. 4‰ ~ - 13. 5‰) ,边 则原始伟晶岩熔体的硼同位素组成应该与区内哈巴河群云
缘带电气石硼同位素组成变化范围较大( δ B = - 15. 4‰ ~
11
母片岩类似,这与本文伟晶岩硼同位素组成显著轻于哈巴河
- 12. 9‰) 且总体偏重。考虑到伟晶岩边缘带受到围岩的影 群云母片岩的事实不符。所以,我们推测云母片岩可能不是
响( 见前述边缘带电气石在微量元素和氧逸度上与内部电气 伟晶岩的唯一源区,即伟晶岩的源区可能有相当比例的黏土
石的差别) ,我们认为其硼同位素的上述特征可能与围岩的 岩。因为黏土岩在变质过程中,吸附 B 和层间 B( 相对富集
11
相互作用有关。 重 B) 在部分熔融发生前逐渐丢失,黏土岩最终主要转变成
11
青河地区未蚀变云母片岩中电气石 δ B = - 13. 1‰ ~ 富含白云母的片岩,而白云母( 结构 B 为主) 具有富集轻硼
- 12. 2‰ ( Zheng et al. ,2022) ,细粒蚀变围岩电气石 δ B = 11
同位素的特 征 ( - 18. 8 ± 0. 8‰; Williams et al. ,2001 ) 。所
- 12. 5‰ ~ - 12. 0‰,即围岩电气石硼同位素显著重于伟晶 以,伟晶岩源区一定含量黏土岩的存在,可能是导致伟晶岩
岩电气石。所以,可以认为伟晶岩内部( 过渡带和核部带) 电 硼同位素显著轻于云母片岩的原因。该成因模型与 Zhao et
气石的硼同位素组成可能更接近原始伟晶岩浆的硼同位素 al. ( 2022) 对川西甲基卡伟晶岩的锶同位素研究一致,后者
特征。这与带状蚀变围岩的电气石硼同位素组成变化范围 发现甲基卡伟晶岩的锶同位素比值显著高于区内云母片岩,
11
大( δ B = - 15. 6‰ ~ - 11. 6‰) 是一致的,后者可以合理地 说明云母片岩不是伟晶岩的唯一源区,而源区黏土岩( 具有
解释为伟晶岩出溶流体与围岩相互作用的结果( 带状蚀变围 高 Rb / Sr 比值和高放射成因 Sr; Lin et al. ,
2020) 的存在可合
岩的电气石主微量元素成分多介于伟晶岩电气石和细粒-粗 理解释伟晶岩的锶同位素特征。
粒蚀变围岩电气石之间; 图 5、图 7) 。青河伟晶岩各分带电 青河伟晶 岩 仅 发 育 较 小 规 模 的 蚀 变 围 岩 ( 宽 度 30 ~
11
气 石 的 δ B 相 差 不 大,主 要 变 化 范 围 为 - 14. 8‰ ~ - 50cm) ,这与西昆仑大红柳滩和川西甲基卡锂矿化伟晶岩的
14. 4‰,明显轻于哈巴河群云母片岩电气石硼同位素组成 围岩都发生强烈蚀变形成鲜明对比 ( 周兵等,2011; 付小方
11
( δ B = ~ - 13. 1‰ ~ - 12. 2‰; Zheng et al. ,2022) ,二者硼 2014) ,围岩强烈蚀变表明含矿伟晶岩演化晚期有大量
等,
同位素分馏差 > 1. 5‰,其原因可能有两个,具体如下: H2 O 流体出溶。类似的例子如 Kings Mountain 锂辉石伟晶岩
( 1) 伟晶岩浆演化晚期发生流体出溶。实验岩石学结果 围岩发生强烈的蚀变( Kesler et al. ,2012) 。所以,矿化伟晶
表明,重硼同位素(
11
B) 更倾向于进入流体相( Meyer et al. , 岩体系可能含大量 H2 O 流体,并对锂矿化起重要作用,而贫
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