Geochemistry of clinopyroxene and chrome spinel in the Zhaheba peridotite, Eastern Junggar, Xinjiang, China and its chromitite metallogenesis
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摘要:
扎河坝蛇绿岩是东准噶尔地区一条重要的蛇绿岩带，主要由橄榄岩、层状辉长岩、玄武岩、斜长花岗岩、硅质岩等组成。其中橄榄岩主要由方辉辉橄岩（方辉橄榄岩）、二辉橄榄岩和少量纯橄岩组成。二辉橄榄岩中的单斜辉石Cr2O3平均1.11%，Al2O3平均4.77%，MgO平均16.99%，CaO平均21.84%，SiO2平均50.00%；铬尖晶石副矿物具有较低的Cr2O3（平均40.35%）、Cr#（平均0.53）和更高的Al2O3（平均24.10%），MgO（平均13.23%）和Mg#（0.62）含量，属高Al型，橄榄岩形成于扎河坝洋扩张时期（MOR环境）；块状铬铁矿铬尖晶石各元素含量变化较小：Cr2O3平均55.45%，Al2O3平均10.88%，MgO平均11.98%和Mg#为0.60，属SSZ背景高Cr型铬铁矿。二辉橄榄岩单斜辉石具有典型的熔融残余结构和熔-岩反应结构，斜方辉石保留绢石化假晶和部分未蚀变的辉石残余体（主要是顽火辉石），铬尖晶石副矿物具有熔蚀特征。单斜辉石的熔融残余结构是含铬矿物熔融、释放铬的一种表现，是橄榄岩部分熔融程度升高，向更富镁方向演化的结构标志，但可能对富Cr型铬铁矿的形成贡献有限。橄榄岩存在熔-岩反应新生的单斜辉石、橄榄石及结构标志。熔-岩反应过程中流体、挥发分的作用不可忽视。文章还探讨了铬铁矿Cr#、Mg#和Al2O3含量差异与蛇绿岩形成的构造背景关系及影响因素。卡拉麦里洋壳俯冲和地幔对流循环使扎河坝早期形成于MOR环境的富Al铬尖晶石富集，形成高Cr块状铬铁矿。
Abstract:Zhaheba ophiolite is a significant ophiolite complex in Eastern Junggar, consisting mainly of peridiotite, basalt, layered gabbro, plagiogranite and chert. Among them, the peridiotite is mainly composed of harzburgite, herzolite, and minor dunite. The average contents of clinopyroxene in herzolite are Cr2O3 1.11%, Al2O3 4.77%, MgO 16.99%, CaO 21.84%, SiO2 50.00%, and the accessory mineral chromium spinel falling within the high-Al types has lower average contents Cr2O3 40.35%、Cr# 0.53 but higher Al2O3 24.10%, MgO 13.23% and Mg#(0.62), which indicate that it was formed during the extension of Zhaheba ocean in MOR environment. While the element contents of chrome spinels in massive chromites changes little with average contents of Cr2O3 55.45%、Al2O3 10.88%, MgO 11.98% and Mg# 0.60, which fall in high-Cr type fields and belong to SSZ type of chromites. Clinopyroxenes in herzolite is characterized by typical structures of melted residue and melt-rock reaction, and orthopyroxene in harzburgite kept bastitic pseudomorphs and unaltered enstatites, but chrome spinel accessory minerals show corrosion features. The melting residual structure of monocline is a manifestation of the melting and chromium release of chromium-bearing minerals, and also a structural indicator of the partial melting degree of peridotite increasing and the evolution towards more magnesium rich direction, which may have limited contribution to the formation of Cr-rich chromite. The peridotite contains monoclinopyroxene, olivine and textures newly generated from melt-rock reaction. The role of fluid and volatiles in the melt-rock reaction cannot be ignored. Based on the above studies, the relationship among the content differences of Cr#、Mg# and Al2O3 of chromite and tectonic settings of ophiolite, and its influence factors are discussed. It is concluded that mantle convection and subduction of Kalamaili ocean led to the enrichment of the high-Al chrome spinels in MOR environment and forming of massive chromites.
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1. 研究目的（Objective）
甘肃省高台县大青山地区地处阿拉善地块龙首山基底杂岩带，位于酒东盆地马营凹陷东段山前沉积盆地北缘（图 1a）。区内主要出露有古元古界—新太古界龙首山岩群、中元古界蓟县系墩子沟群、海西期侵入岩、侏罗系龙凤山组和白垩系庙沟组（图 1b）。
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图 1 甘肃省高台县大青山地区大地构造位置图（a）、区域地质图（b）以及ZK1201岩性柱状图（c），含油气岩心照片（d-g）和油气成藏模式图（h）Figure 1. Tectonic location (a), regional geological map(b), lithology column(c) and drill photos of ZK1201 (d-g), hydrocarbon accumulation pattern (h) in the Daqingshan area of Gaotai County, Gansu Province为实现研究区金属资源和油气资源的综合调查，中国地质调查局发展研究中心联合甘肃省地调院、探矿工程所、吉林大学在前期“甘肃省高台县臭泥墩—西小口子地区三幅1∶5万矿产远景调查”项目基础上，通过开展专题地质填图、矿产综合信息预测、智能找矿预测等工作，部署实施钻孔ZK1201，以期实现找矿突破。
2. 研究方法（Methods）
利用研究区地质调查、磁法、激电测深、化探数据和无人机影像等资料，开展综合信息解译。采用卷积和孪生网络神经网络模型对区内典型金属矿床成矿作用特征标志、油气赋矿层位进行深度学习，提出工程验证建议。钻探验证所采用钻机为汽车钻，整机包括车底盘、动力系统、液压系统、操控系统等。
3. 结果（Results）
在综合研究和智能预测的基础上，布设的ZK1201孔在钻穿早二叠世花岗闪长岩（图 1c）后，钻遇地层，续钻至393.8 m后终孔（图 1c）。此次工作共钻遇中侏罗统龙凤山组地层220 m，共发现14层油层（总厚145 m，单层最大厚度28 m，最小厚度1.4 m）。钻孔含油性由上部砾岩（油斑级以下）向下部砂岩（富含油或饱含油）逐渐增多，其中高角度裂缝普遍见可流动原油（图 1d~g）。经国家地质实验测试中心分析，原油中饱和烃、芳烃含量分别占32.4%和34.6%，为高品质轻质原油。原油中正构烷烃分布完整，主峰碳数、奇偶优势及甾烷和藿烷分布都指示其陆相烃源岩来源。
野外地质调查发现，白垩系庙沟组近水平发育，与下伏侏罗系龙凤山组呈角度不整合接触。庙沟组主要由厚层暗色泥岩组成，并发育薄层暗色粉砂质泥岩，可能为区域烃源岩层。初步判断成熟的烃源岩排出的油气沿角度不整合运移至侏罗系砂砾岩和砂岩储层后，被逆冲推覆花岗岩体封闭，形成构造-岩性油气藏（图 1h）。
研究发现区域内沉积盆地最南缘边界处在祁连山北缘断裂之下，最北缘处在龙首山断裂的下盘，南北跨度约80 km。区域内沉积地层较厚，其中侏罗系龙凤山组厚约2100 m，白垩系庙沟组厚约900 m，说明研究区具有较大的成藏潜力。此次油气藏的发现，预示着大青山地区具有完整的油气成藏系统，显示出良好油气勘探前景。建议进一步加强油气基础地质调查研究工作。
4. 结论（Conclusions）
（1）在大青山地区花岗岩逆冲推覆体之下的中生代沉积地层中发现原油，所发现的高品质轻质原油，具陆相烃源岩来源特征。
（2）研究区具有良好的油气勘探前景，建议进一步加强油气地质调查研究工作。
5. 致谢（Acknowledgement）
感谢甘肃省地质调查院董国强，北京探矿工程研究所渠洪杰、谭春亮以及国家实验测试中心沈斌在野外工作和样品测试过程中的协助。
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图 1 研究区构造单元图（据新疆地矿局修改❶）
Ⅰ—西伯利亚板块；Ⅰ-1—阿尔泰活动陆缘带；Ⅰ-1-1—清河中间地块；Ⅰ-1-2—震旦纪边缘海盆；Ⅰ-1-3—乌恰沟-玛因鄂博晚古生代岛弧带；Ⅱ—哈萨克斯坦—准噶尔板块；Ⅱ-1—准噶尔北缘构造带；Ⅱ-1-1—二台晚古生代复合岛弧带；Ⅱ-1-2—乌伦古二叠纪上叠盆地；Ⅱ-1-3—扎河坝—二台古生代沟弧带；Ⅱ-1-4—库兰卡孜干晚古生代岛弧带；Ⅱ-1-5—东准噶尔晚古生代陆缘盆地；EMT—额尔齐斯-玛因鄂博缝合带
Figure 1. Tectonic division map of the study area (modified from Xinjiang Bureau of Geology and Mineral Resources)
Ⅰ-Siberian plate; Ⅰ-1-Altai active marginal zone; Ⅰ-1-1-Qinghe intermediate massif; Ⅰ-1-2-Sinia marginal basin; Ⅰ-1-3-Wuqiagou-Mayinebo late Paleozoic island arc belt; Ⅱ-KazakhstanJunggar Plate; Ⅱ-1-Northern margin of Junggar tectonic belt; Ⅱ-1-1-Ertai late Paleozoic composite island arc belt; Ⅱ-1-2-Wulungu Permian superimposed basin; Ⅱ-1-3-Zhaheba-Ertai Paleozoic trencharc belt; Ⅱ-1-4-Kulankazigan late Paleozoic island arc belt; Ⅱ-1-5-East Junggar late Paleozoic continental margin basin; EMT-ErtixMayinebo suture zone
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图 3 扎河坝铬铁矿矿石照片
a—6号铬铁矿点角砾状、块状铬铁矿(ZHB-b40)；b—铬尖晶石显微照片(ZHB-b40)；c—3号铬铁矿点地表块状铬铁矿体；d—3号铬铁矿点浅井内块状铬铁矿；e—3号铬铁矿点块状铬铁矿显微照片(ZHB-b56)
Figure 3. Photoes and photomicrographs of Zhaheba chromite ore
a-No.6 chromite spot brecciated and massive chromite (ZHB-B40); b-Microphotograph of chrome spinel (ZHB-B40); c-Surface massive chromite orebody at No. 3 ore occurrence; d-Mmicrophotograph of massive chromite at the No. 3 ore occurrence (ZHB-B56)
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图 4 扎河坝橄榄岩显微照片
a—ZHB-15样品方辉橄榄岩内铬尖晶石和新生橄榄石（正交偏光）；b—Z19-26样品二辉橄榄岩斜方辉石残余、新生橄榄石和橄榄石残留晶（单偏光）；c—Z19-25样品蛇纹石化二辉橄榄岩内熔融残余结构、新生橄榄石、新生的单斜辉石（正交偏光）；d—Z19-25样品蛇纹石化二辉橄榄岩内新生的橄榄石、单斜辉石（正交偏光）；e—D363样品二辉橄榄岩内熔融残余结构、新生单斜辉石（正交偏光）；f—Z19-25样品蛇纹石化二辉橄榄岩内新生的橄榄石和单斜辉石（正交偏光）；g—D363样品二辉橄榄岩内熔融残余结构、反应边结构（正交偏光）；h—D363样品二辉橄榄岩熔融残余结构（反射光）。Opx—斜方辉石；Cpx—单斜辉石；Ol—橄榄石；Bas—绢石；Sp—尖晶石；Serp—蛇纹石；Ol2—新生橄榄石；Cpx2—新生的单斜辉石；BMS—贱金属硫化物
Figure 4. Microphtographs of Zhaheba peridotite
a-Chrome spinel and new olivine in harzburgite, cross-polar (ZHB-15); b-Orthopyroxene relicts, new olivine and olivine relicts in lherzolite, plane-polar (Z19-26); c-Structure of melted residual, new olivine, new clinopyroxene in serpentinized lherzolite, cross-polar (Z19-25); d-New olivine, new clinopyroxene in serpentinized lherzolite, cross-polar (Z19-25); e-Structure of melted residual, new clinopyroxene in lherzolite, cross-polar (D363); f-New olivine, new clinopyroxene in serpentinized lherzolite, cross-polar (Z19-25); g-Structure of melted residual, reactionrim texture in in lherzolite, cross-polar (D363); h-Structure of melted residual in lherzolite, cross-polar, reflected light (D363). OpxOrthopyroxene; Cpx-Clinopyroxene; Ol-Olivine; Bas-Bastite; Sp-Spinel; Serp-Serpentine; Ol2-New olivine; Cpx2-New clinopyroxene; BMSBase metal sulfides
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图 5 橄榄岩尖晶石副矿物、块状铬铁矿镜下照片及背散射图像
a（正交偏光）、b（反射光）—D15样品方辉橄榄岩内新生单斜辉石及铬尖晶石边部发生磁铁矿化；c—ZHB-b15样品方辉橄榄岩内半自形铬尖晶石及不规则状铬尖晶石残留；d—3号铬铁矿点ZHB-b40样品角砾状铬铁矿反射光照片；e—D357样品方辉橄榄岩内铬尖晶石熔蚀结构背散射（BSE）照片；f、h—D15样品方辉橄榄岩背散射（BSE）照片，尖晶石副矿物熔蚀结构及其边部、裂隙处铁铬铁矿（Fe-chr）；g—3号铬铁矿点碎裂状、块状铬铁矿尖晶石背散射（BSE）照片；Cpx—单斜辉石；Bas—绢石；Cr—铬铁矿；Serp—蛇纹石；Cal—碳酸盐；Cpx2—新生单斜辉石；Fe-chr—铁铬铁矿；Mag—磁铁矿
Figure 5. Microphtograph of spinel in peridotite and back scattered electron images (BSE) of spinels in massive chromite
a (cross-polar), b (reflected light)-New clinopyroxene, magnetization occurs at the edge of chrome spinel in harzburgite (D15); c-Subhedral chrome spinel, irregular chrome spinel relicts in harzburgite, reflected light (ZHB-b15); d-Photomicrographs of brecciaous chromitite in No. 3 chromite point, reflected light (ZHB-b40); e-BSE images of chrome spinel with melting corrosion structure in harzburgite (D357); f, h-BSE images of chrome spinel with melting corrosion structure, altered to ferritchromite (Fe-chr) along it's cracks and edges in harzburgite (D15); gBSE images of chrome spinel of fractured, massive chromites in No.3 chromite point; Cpx-Clinopyroxene; Bas-Bastite; Cr-Chromite; SerpSerpentine; Cal-Carbonate; Cpx2-New clinopyroxen; Fe-chr-Ferritchromite; Mag-Magnetite
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图 6 单斜辉石主要氧化物关系图解
Figure 6. Diagram showing the relationship among major oxides of the clinopyroxene
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图 7 橄榄岩内尖晶石副矿物、块状铬铁矿尖晶石Al2O3-Cr2O3含量（%）图解
（层状铬铁矿、豆荚状铬铁矿数据范围参考Bonavia et al., 1993；土耳其高Cr、高Al铬铁矿数据范围参考Uysal et al., 2009；埃及CED铬铁矿数据范围参考Ahmed et al., 2001；萨尔托海数据范围参考Zhou et al., 2014；罗布莎数据范围参考周二斌等, 2011, 下同）
Figure 7. Al2O3 versus Cr2O3(%) diagram of spinels in peridotite and massive chromite
Compositional fields of stratiform and podiform chromitites are from Bonavia et al., 1993; High-Cr and high-Al compositional fields of SW Turkey (Uysal et al., 2009); Central and southern Eastern Desert (CED, SED) of Egypt (Ahmed et al., 2001); Compositional fields of Sartohay (Zhou et al., 2014); Compositional fields of Luobusha (Zhou, 2011)
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图 8 橄榄岩内尖晶石副矿物、块状铬铁矿尖晶石Cr#-Mg#（Mg/(Mg+Fe+2)）关系图解
High Cr，High Al和High Fe数据范围引自Zhou and Bai (1992)；豆荚状铬铁矿、层状铬铁矿和Alpine型范围参考Irvine (1967)和Leblanc and Nicolas (1992)；玻安岩范围参考Arai (1992)，abyssal橄榄岩范围参考Dick and Bullen (1984)；弧后环境橄榄岩范围参考Monnier et al.（1995），SSZ环境橄榄岩范围参考Choi et al.（2008），萨尔托海铬铁矿数据引自Zhou et al，2014；罗布莎铬铁矿数据周二斌等（2011）
Figure 8. Cr# versus Mg#(Mg/(Mg+Fe+2)) diagram of spinels in peridotite and massive chromite
Compositional fields of High Cr, High Al and High Fe are from Zhou and Bai (1992); The podiform, stratiform fields and Alpine-type field are from Irvine (1967) and Leblanc and Nicolas (1992); The boninite field is from Arai (1992). The abyssal peridotite field is from Dick and Bullen (1984); Back-arc Peridotite field is from Monnier et al. (1995); SSZ peridotite field is from Choi et al. (2008); Compositional fields of Sartohay (Zhou et al, 2014); Compositional fields of Luobusha (Zhou E B et al, 2011)
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图 9 橄榄岩内尖晶石副矿物、块状铬铁矿尖晶石Cr/Fe-Cr#关系图解
分区范围参考Rammlmair (1986)，Günay and Çolakoğlu (2016), 萨尔托海铬铁矿数据引自Zhou et al., (2014)；罗布莎铬铁矿数据周二斌等（2011）
Figure 9. Cr# versus Cr/Fe diagram of spinels in peridotite and massive chromite
Compositional fields are from Rammlmair (1986), Günay and Çolakoğlu (2016), Compositional fields of Sartohay Zhou et al. (2014); Compositional fields of Luobusha (Zhou E B et al, 2011)
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图 10 扎河坝蛇绿岩及铬铁矿形成演化示意图
a—扎河坝—阿尔曼泰洋拉张，地幔上涌，形成地幔橄榄岩，铬铁矿预富集，扎河坝洋洋壳俯冲；b—卡拉麦里洋壳俯冲，地幔对流循环和俯冲带上盘块状铬铁矿形成
Figure 10. Schematic illustration showing formation and evolution of Zhaheba ophiolite and chromite
a-Stretching of Zhaheba-Aermantai ocean, followed by mantle upwelling, forming of mantle peridotite, chromite preenrichment, and subduction of Zhaheba Oceanic; b-Subduction of Karamaili ocean, accompanied by mantle convection and recycling, forming of massive chromite in supra-subduction zone (SSZ)
表 1 块状铬铁矿内铬尖晶石及橄榄岩铬尖晶石副矿物、单斜辉石电子探针数据（%）及参数统计
Table 1 Electron microprobe analyses of spinels in massive chromite and peridotite and clinopyroxene
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