Study on Petrological and Mineralogical Characteristics of the Ningxia Helan Stone by X-ray Fluorescence Spectrometry and X-ray Diffraction
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摘要: 宁夏贺兰石是中国砚用名石之一，开发应用越来越广泛，对其进行系统的基础研究具有重要的现实意义。但目前仅有初步的人工实验，缺乏系统的矿物学研究。本文采用常规宝玉石学测试结合薄片鉴定、X射线荧光光谱、X射线粉晶衍射等矿物谱学分析测试方法，解析贺兰石的宝石学特征、化学成分、岩石结构及矿物组成特征。结果表明：贺兰石主要组成矿物为水云母~绢云母，次为褐铁矿(氧化铁质)、石英(砂质碎屑)、绿泥石和微量的赤铁矿、金红石、电气石等；主要化学成分为SiO2、Al2O3、TFe2O3、K2O、MgO、TiO2、CaO、P2O5；折射率1.56~1.57，密度2.81~2.86 g/cm3，摩氏硬度3~4。初步探讨了贺兰石致色成因，基于Fe元素形态及含量与贺兰石颜色具相关关系，认为Fe元素是宁夏贺兰石致色的主要因素。本研究基本确定了贺兰石的大部分特征参数，为后续建立准确的命名及鉴定方法提供了技术支撑。Abstract: The Ningxia Helan Stone is one of the well-known stones that are used for making inkslab in China. The development and application of Helan Stone is becoming more and more widespread, and therefore, it is necessary to carry out a systematic study. At present, there are only preliminary artificial experiments and systematic study of mineralogy is lacking. The conventional gemological test method is combined with spectroscopic analytical methods such as optical thin section identification, X-ray Fluorescence Spectrometry (XRF), X-ray Powder Diffraction (XRD) to study the gemological characteristics, chemical components, rock structure, and the mineral compositions of the Ningxia Helan Stone and is reported in this paper. The results show that the minerals of the Ningxia Helan Stone include major hydromica and sericite, and minor ferric oxide, sandy clastics, chlorite, and trace amounts of hematite, rutile, and tourmaline. The Ningxia Helan Stone has chemical components including SiO2, Al2O3, TFe2O3, K2O, MgO, TiO2, CaO, P2O5, a refractive index of 1.56-1.57, a density of 2.81-2.86 g/cm3, and a mohs hardness of 3-4. The main color-causing factor of the Ningxia Helan Stone is also discussed. Based on the correlation between the morphology and content of Fe element and the color of the Helan stone, it is considered that Fe is the main color-causing element. The most characteristic parameters of Ningxia Helan Stone have been determined in this study, which provides technical support for follow-up accurate nomenclature and identification method for the Helan Stone.
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表 1 贺兰石样品描述及宝石学测试数据
Table 1. The sample description and gemological data for the Helan Stone
测试样品 样品H-8 样品H-10 样品H-12 样品H-13 样品H-14 
外观描述 灰绿色-灰紫色，不透明，质地极细(测试灰绿色部位) 灰紫色基质，圆斑状、团块状灰绿色，不透明，质地较细 灰紫色基质，偶见圆斑状灰绿色，不透明，质地较粗，夹0.5 mm的砂线 灰紫色基质，不规则状灰绿色，不透明，质地较细 灰紫色基质，带状、串珠状灰绿色，不透明，质地较细 折光率(点测) 1.57 1.56 1.56 1.56 1.56 密度(g/cm3) 2.84 2.84 2.86 2.82 2.81 摩氏硬度 3~4 3~4 3~4 3~4 3~4 
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表 2 贺兰石样品化学成分
Table 2. Chemical compositions of the Helan Stone
元素 各样品中元素分析含量(%) H-8 H-10 H-12 H-13 H-14 平均值 SiO2 60.66 58.22 59.38 58.04 58.60 58.98 Al2O3 16.29 16.09 15.72 16.12 15.66 15.98 TFe2O3 7.75 9.24 9.08 9.49 9.94 9.1 K2O 7.05 7.07 6.91 7.11 6.98 7.02 MgO 1.58 1.75 1.58 1.56 1.64 1.62 CaO 0.49 0.43 0.41 0.71 0.54 0.52 TiO2 0.83 0.87 0.85 0.86 0.90 0.86 Na2O 0.16 0.12 0.12 0.2 0.12 0.14 P2O5 0.14 0.13 0.14 0.15 0.14 0.14 BaO 0.039 0.037 0.035 0.036 0.035 0.04 Cl 0.007 0.005 0.009 0.007 0.009 0.01 V 0.013 0.012 0.012 0.012 0.011 0.01 Cr 0.009 0.009 0.010 0.010 0.010 0.01 Ni 0.004 0.005 0.004 0.004 0.004 0.004 Rb 0.020 0.020 0.019 0.020 0.020 0.02 Zr 0.016 0.016 0.018 0.017 0.016 0.017 总计 95.06 94.02 94.30 94.35 94.63 94.47 Fe2O3(容量法) 6.74 8.32 8.19 8.55 8.96 8.15 FeO(容量法) 1.01 0.92 0.89 0.94 0.98 0.95 烧失量(重量法) 3.78 4.32 3.91 4.02 3.66 3.97
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表 3 贺兰石X射线衍射分析结果
Table 3. X-ray diffraction data of the Helan Stone
样品编号 样品中矿物半定量结果(%) 石英 云母 褐铁矿 斜绿泥石 赤铁矿 H-8 35.1 53.3 7.3 4.4 (0.5) H-10 32.4 53.6 10.1 3.2 (0.7) H-12 34.0 51.5 9.2 3.0 1.1 H-13 36.9 51.0 9.0 3.1 (0.4) H-14 36.2 52.3 9.4 2.7 (0.6)
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