Study on the mineralogical characteristics of crystalline graphite from Xiangshan graphite deposit in Huaining County, Anhui Province
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摘要:
文章运用多种分析测试方法及研究手段，首次对安徽怀宁地区象山石墨矿床开展了晶质石墨矿物学特征研究。象山矿床的晶质石墨具有完整的晶型，呈鳞片状集合体；能谱分析结果显示，晶质石墨中的碳原子含量为91.99%～92.74%；激光拉曼分析结果显示，石墨具有较高的结晶度和有序且完整的碳原子结构，其激光拉曼特征图谱缺失D1峰和D2峰，与石墨烯的激光拉曼图谱具有较高的相似性；粉晶衍射分析结果反映了晶质石墨具有2H型石墨特征，轴长a=0.246 1～0.246 6 nm，c=0.669 3～0.670 0 nm，晶胞体积V=0.035 1～0.035 29 nm3。石墨鳞片厚度为37.1～43.3 nm，石墨化度为82～96，估算其成矿变质温度为542.4～587.2 ℃，3R多型含量为9.03%～10.37%，δ13C值为−29.223‰～−26.926‰，表明石墨碳质来源于地层中同源沉积的生物有机碳质，更接近泥碳及现代有机质的含量水平，可能不存在岩浆带入的含碳流体及碳酸盐岩分解的无机碳。
Abstract:In this paper, the researchers have employed a variety of analytical testing methods and research techniques to conduct the first study on the crystalline graphite mineralogical characteristics of Xiangshan graphite deposit in Huaining County, Anhui Province. The crystalline graphite of the Xiangshan deposit has a relatively complete crystal form and appears as flake aggregates. Energy spectrum analysis shows that the content of C atom in the crystalline graphite ranges from 91.99% to 92.74%. Laser Raman spectroscopy shows that graphite has a high degree of crystallinity and an orderly complete carbon atomic structure. Its laser Raman characteristic spectrum lacks D1 and D2 peaks, similar to the Raman spectroscopy in graphene. Powder X-ray diffraction (XRD) reveals that the crystalline graphite exhibits characteristics of 2H type graphite, with an axis length a=0.246 1～0.246 6 nm, c=0.669 3～0.670 0 nm, and a unit cell volume V=0.035 1～0.035 29 nm3. The thickness of graphite flake varies from 37.1～43.3 nm, the degree of graphitization 82～96, the estimated metamorphic temperature 542.4～587.2 ℃, the content of 3R polymorphism 9.03%～10.37% and δ13C value −29.223‰～−26.926‰. These findings all suggest that the graphite carbon derived from bio-organic carbon deposited in the strata, which is closer to the level of peat and modern organic matter. Besides, there is no evidence of carbon-containing fluid brought in by magma and inorganic carbon resulting from carbonate rock decomposition.
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图 5 象山石墨与其他碳质的碳同位素组成对比（Hoefs, 2009；姜高珍, 2016；姜高珍等, 2017；兰心俨, 1981；李小东等, 2022；毋应科, 2022）
Figure 5.
表 1 怀宁象山地区与我国其他典型地区的晶质石墨拉曼特征参数对比
Table 1. Comparison of Raman characteristic parameters of crystalline graphite between Xiangshan of Huaining and other typical areas in China
地区 样品编号 G峰位置/cm−1 D峰位置/cm−1 G´峰/cm−1 R 数据来源 峰位 半高宽 峰位 半高宽 峰位 半高宽 怀宁象山 ZK201b 1 577.62 18.04 1 346.62 42.30 2 706.41 74.10 0.04 本文 ZK61b 1 575.79 15.94 — — 2 705.82 70.81 — ZK72b 1 576.27 17.97 — — 2 707.89 63.30 — ZK1001b 1 577.44 16.87 — — 2 709.28 68.74 — 内蒙古兴和 XH80G 1 581.7 15.83 1 346.38 2.26 — — 0.03 鲜海洋等，2015 黑龙江鸡西 J892G 1 581.7 15.42 1 372.52 4.84 — — 0.02 
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表 2 怀宁象山与我国其他地区石墨的晶胞参数对比
Table 2. Comparison of cell parameters of graphite in Xiangshan area of Huaining and other areas in China
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表 3 怀宁象山与其他典型石墨矿石墨样品XRD特征及反演参数统计对比
Table 3. Statistical comparison of XRD characteristics and inversion parameters of graphite samples from Xiangshan, Huaining and other typical graphite mines
产地 样品编号 β(002)/° 2θ/° d002/ nm Lc(002)/nm DG 温度/℃ 数据来源 怀宁象山 ZK61-b 0.203 26.568 0.335 2 43.3 96 587.2 本文 ZK201-b 0.237 26.625 0.334 8 37.1 82 542.4 内蒙古大乌淀 D01 0.190 26.610 0.334 7 42.5 95 584.0 姜高珍等，2017 安徽凤阳 JSZK3506 0.213 26.487 0.336 2 28.8 74 516.0 李小东等，2022 湖南鲁塘 0.324 26.438 0.335 8 43.45 95 — 杨瑞，2021
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表 4 典型石墨矿床和象山石墨样品的石墨化度与菱面体多型含量
Table 4. Graphitization degree and 3R polytype content of typical graphite deposits and Xiangshan graphite samples
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表 5 怀宁象山与内蒙古大乌淀石墨的δ13C分析结果对比
Table 5. Comparison of carbon stable isotope analysis results of graphite between Xiangshan of Huaining and Dawudian of Inner Mongolia
地区 样品编号 石墨产出特征 同位素组成（δ13C/‰） 数据来源 怀宁象山 ZK61-b 角岩中鳞片状石墨 −27.867 本文 ZK201-b 角岩中鳞片状石墨 −26.926 ZK1001-b 角岩中鳞片状石墨 −29.223 ZK72-b 角岩中鳞片状石墨 −27.354 内蒙古大乌淀 鳞片状石墨 −28.6～−29.4 姜高珍等，2017
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