Determination of Composition of Pyrite in the Baishantang Copper Deposit by Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry and Electron Microprobe
-
摘要: 通过激光剥蚀电感耦合等离子体质谱（LA-ICP-MS）获得被测物相中痕量元素的丰度值是目前原位分析矿物物相的技术之一。黄铁矿作为斑岩铜矿中的重要矿物，其主量、微量元素的特征能为成矿过程提供重要信息。本文建立了应用LA-ICP-MS测定黄铁矿微区微量元素组成、电子探针（EMPA）测定主量元素的方法，并将该方法应用到白山堂斑岩铜矿区。LA-ICP-MS实验采用60 μm的激光束对分析样品进行斑点式剥蚀，以氦气作载气，重复频率5 Hz，激光能量约6 J/cm2；单点分析时间60 s，分析数据以Fe作内标，用MASS-1黄铁矿标样进行校正，多数元素分析精度好于10%。针对黄铁矿与毒砂光学性质相似，容易混淆的问题，可以利用二者物理性质的差异进行区分。测试结果显示：矿区黄铁矿的主量元素呈亏硫高铁的特征，指示其为热液成因；微量元素特征表明其形成深度为中部，属与火山作用有关的中低温热液型黄铁矿。此结论对白山堂铜矿的成因类型、成矿流体来源等提供了相应的证据，对矿区的勘查具有理论指导意义。
-
关键词:
- 黄铁矿 /
- 白山堂铜矿 /
- 激光剥蚀电感耦合等离子体质谱 /
- 电子探针 /
- 主量和微量元素
Abstract: Determination of trace elements in analyzed mineral phase by Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS) is a new in situ technique for mineral phase analyses. As an important mineral in porphyry copper deposits, the major and trace elements of pyrite can provide important information for the ore-forming process. A method for determination of the trace elements in pyrite by LA-ICP-MS and major elements by Electron Microprobe was developed and has been applied to the Baishantang porphyry copper ore district. For the LA-ICP-MS experiment, the laser beam is 60 μm, the carrier gas is helium, the repetition frequency is 5 Hz, the laser energy is 6 J/cm2, and the analysis time of single point is 60 s. Iron was used as an internal standard and MASS-1 was used to calibrate the data. Analysis precision of most elements is better than 10%. For the similar optical properties of pyrite and arsenopyrite, the differences of physical properties can be used to distinguish them. Pyrite in the Baishantang porphyry copper deposit is depleted in sulfur but rich in iron, indicating a hydrothermal origin. The trace element composition of pyrite indicates that pyrite was formed at a medium depth and belongs to the medium-low temperature hydrothermal type related to volcanism. This conclusion has provided important evidence for the ore genesis and the source of ore-forming fluids of the Baishantang porphyry copper deposit, which can also guide the next-step exploration. -
-
表 1 MASS-1标样分析误差
Table 1. The analytical error of MASS-1 standard sample
元素 推荐值 (μg/g) 19次测定的平均值 (μg/g) 相对误差 (%) RSD (%) Co 66 66.2 0.31 3.84 Ni 89 89.6 0.7 5.92 Cu 134000 134000 0 3.16 Pb 73 73.6 0.79 4.48 Zn 210000 209980 0.01 7.97 Au 47 47.8 1.72 9.09 Ag 52 52 0.02 2.36 Mo 55 55.4 0.65 3.76 Bi 59 59.3 0.45 1.99 Sn 57 57.2 0.36 2.15 Sb 57 57.8 1.33 7.31 Te 18 17.7 1.7 12.43 As 56 56.6 1.03 17.8 Se 47 45.1 3.96 16.49 Cd 73 73.5 0.63 10.38 
下载: 导出CSV
表 2 白山堂斑岩铜矿黄铁矿中的主要元素和微量元素分析结果
Table 2. Analytical results of major and trace elements in pyrite from Baishantang ore deposit
样品编号 探针分析的主要元素的含量(%) LA-ICP-MS分析的微量元素的含量(μg/g) Fe S Co Ni Cu Zn As Se Mo Ag Cd Sn Sb Te Au Pb Bi S/Se Co/Ni BST12-8-1 46.68 53.48 200 38.2 2.04 1.2 11.9 15.3 1.95 0.56 - 1.63 0.69 - - 9.85 5.03 3.49 5.24 BST12-8-2 46.29 52.85 636 147 880 1.48 161 10.1 4.52 22.6 3.36 186 23.2 - 0.15 382 6.89 5.26 4.32 BST12-8-3 46.50 52.82 436 99.8 477 2.23 36.0 12.5 0.2 3.01 - 20.9 1.67 0.9 0.17 193 661 4.22 4.37 BST12-8-4 46.39 53.31 245 50.3 24.3 0.9 13.6 18.0 2.03 0.16 - 0.78 1.72 0.25 - 9.17 11.4 2.96 4.88 BST12-8-5 46.68 51.76 122 40.6 82.5 2.56 39.6 12.8 0.03 2.08 0.13 10.1 0.74 - - 65.6 0.23 4.05 3.01 BST12-8-6 47.23 52.23 449 210 775 0.75 78.5 14.0 0.59 41.0 1.28 94.1 15.1 - 0.36 1197 9.33 3.73 2.14 BST12-8-7 46.95 52.96 381 89.9 207 1.08 32.8 7.45 0.48 2.33 1.57 24.9 3.26 - 0.02 250 275 7.11 4.24 BST12-8-8 46.48 52.23 470 101 99.4 2.13 53.0 7.43 6.13 1.5 1.34 25 1.87 - - 45.5 4.94 7.03 4.65 BST12-8-9 46.29 52.06 516 123 118 20.9 36.2 7.51 2.29 1.48 1.82 53.9 3.47 0.37 - 75.7 9.79 6.93 4.21 BST12-8-10 46.85 52.15 551 171 359 0.98 53.5 13.8 1.2 2.65 2.99 28.5 7.47 0.23 0.0037 70.4 158 3.79 3.22 BST12-8-11 46.50 52.40 535 153 430 1.12 76.3 10.9 0.6 3.6 3.56 82.2 8.97 0.25 0.032 94.5 28.2 4.82 3.49 BST12-8-12 46.30 52.80 602 121 572 2.02 174 8.62 2.17 21.1 2.54 138 16.8 - 0.3 546 27.4 6.13 4.97 BST12-8-13 46.49 52.48 650 168 287 2.76 79.6 9.35 3.15 15.6 1.7 70.9 6.82 - 0.13 260 35.6 5.61 3.87 BST12-8-14 46.88 52.60 475 120 791 0.97 95.9 11 0.73 6.83 2.7 96.7 12.8 - 0.11 261 40.9 4.78 3.95 BST12-8-15 46.85 52.29 596 117 556 1.03 188 11.6 3.36 14.6 3.39 135 18.8 - 0.21 408 10.4 4.49 5.11 BST12-8-16 47.08 52.90 121 19.7 - 1.02 9.35 30.2 - 0.14 - 3.86 6.49 - 0.0013 11.3 0.14 1.75 6.14 BST12-8-17 46.31 53.20 1.84 0.92 14.7 0.59 13.9 - 0.33 0.43 0.065 0.83 0.26 - - 1.58 0.02 - 2.00 BST12-8-18 46.73 53.53 4.64 0.7 4.34 1.02 15.6 4.16 4.15 0.068 - 1.51 0.86 - - 2.17 0.42 12.87 6.63 BST12-8-19 46.89 53.66 492 91.2 6.94 1.01 23.0 12.5 0.76 0.85 - 1.13 0.63 - - 23.8 12.3 4.31 5.39 BST12-8-20 46.62 53.61 509 83.3 6.51 0.91 169 14.2 0.63 0.89 - 1.64 0.97 - 0.0087 32.3 55.1 3.79 6.11 BST12-14-1 46.38 52.16 49.8 251 308 15.3 122 - 0.55 5.21 0.028 5.63 8.85 - - 73.7 16.0 - 0.20 BST12-14-2 45.69 51.92 386 211 96.9 67.5 1974 10.7 0.34 0.11 - 7.40 1.95 - - 7.24 4.33 4.84 1.83 BST12-14-3 46.58 51.78 427 1107 2454 4.02 557 17.8 4.79 10.5 8.36 6.94 71.1 - 0.0102 3676 2.89 2.91 0.39 BST12-14-4 47.02 53.34 38.4 116 86.8 3.55 46.9 18.6 0.95 1.33 - 2.03 1.64 - - 58.0 1.491 2.87 0.33 BST12-14-5 47.45 53.14 2.57 96.5 2.71 12.2 5290 35.5 0.47 0.031 - 0.33 2.92 - 0.213 17.5 4.02 1.50 0.03 BST12-14-6 47.18 52.86 40.8 192 173 1.96 25.8 30.5 0.25 2.03 - 0.15 2.77 - - 27.5 0.81 1.73 0.21 BST12-14-7 46.62 52.45 16.0 34.0 75.5 1.46 30.8 10.7 0.99 0.29 0.035 0.39 1.18 - - 52.1 0.55 4.90 0.47 BST12-14-8 47.23 52.14 10.6 51.1 221 15.9 66.6 3.97 1.09 2.28 0.12 1.81 3.17 - - 42.6 15.6 13.13 0.21 BST12-14-9 45.46 51.97 579 617 1159 1.82 2059 19.0 31.8 10.3 16.4 12.8 98.9 - 0.0047 3276 3.73 2.73 0.94 BST12-14-10 46.94 52.37 4551 90.5 938 43.4 887 38.5 0.55 1.96 0.44 1.43 23.6 0.57 0.118 492 133 1.36 50.30 BST12-14-11 46.59 53.67 986 48.2 3959 33.6 807 24.0 0.83 0.12 0.16 25.7 9.73 - 0.0011 13.2 7.98 2.24 20.46 BST12-14-12 47.20 53.40 648 188 84.1 3.52 1616 57.8 0.61 39.8 1.07 0.78 7.49 0.6 0.0074 22467 180 0.92 3.45 BST12-14-13 47.10 53.44 10.1 35.2 145 3.01 22.4 9.39 0.93 1.47 0.067 0.31 1.11 - 0.00161 44.2 1.96 5.69 0.29 BST12-14-14 46.19 53.29 671 202 804 38.6 250 16.6 0.67 0.52 0.022 0.4 1.64 - 0.006 21.3 3.34 3.20 3.32 BST12-14-15 47.15 53.54 197 88.4 - 0.87 3145 35.2 - - - - - - 0.0101 0.137 0.083 1.52 2.22 BST12-14-16 46.47 52.08 240 282 858 1.76 666 30.3 2.74 5.88 7.79 1.79 36.4 - 0.0062 1584 1.45 1.72 0.85 BST12-14-17 46.91 52.49 116 112 382 1.29 282 9.56 1.06 2.12 3.06 3.53 18.5 - - 679 4.15 5.49 1.03 BST12-14-18 46.83 52.26 285 270 626 2.45 394 18.4 3.67 4.18 7.93 2.66 33.2 - - 1509 1.71 2.84 1.05 BST12-14-19 46.07 52.55 215 333 540 2.11 245 23.7 2.82 4.41 4.62 6.45 19.6 - - 1014 5.37 2.22 0.65 注：表格中的“-”代表分析值低于仪器的检出限。
下载: 导出CSV
-
[1] Arehart G B,Eldridge C S,Chryssoulis S L,et al.Ion Microprobe Determination of Sulfur Isotope Variations in Iron Sulfides from the Post/Betze Sediment-hosted Disseminated Gold Deposit,Nevada,USA[J]. Geochimica et Cosmochimica Acta,1993,57:1505-1519. doi: 10.1016/0016-7037(93)90010-T
[2] 严育通,李胜荣,贾宝剑,等.中国不同成因类型金矿床的黄铁矿成分标型特征及统计分析[J].地学前缘,2012,19(4):214-226. http://www.cnki.com.cn/Article/CJFDTOTAL-DXQY201204024.htm
Yan Y T,Li S R,Jia B J,et al.Composition Typomorphic Characteristics and Statistic Analysis of Gold Deposits of Different Genetic Types[J].Earth Science Frontiers,2012,19(4):214-226. http://www.cnki.com.cn/Article/CJFDTOTAL-DXQY201204024.htm
[3] 寇大明,黄菲,姚玉增,等.黄铁矿晶体形貌学研究进展[J].矿物学报,2009,29(3):333-337. http://www.cnki.com.cn/Article/CJFDTOTAL-KWXB200903009.htm
Kou D M,Huang F,Yao Y Z,et al.Progress in the Pyrite Crystal Morphology[J].Acta Mineralogica Sinica,2009,29(3):333-337. http://www.cnki.com.cn/Article/CJFDTOTAL-KWXB200903009.htm
[4] 黄菲,寇大明,宋丹,等.山西耿庄黄铁矿晶须形貌的显微观测及其标型意义[J].地质学报,2011,85(9):1486-1492. http://www.cnki.com.cn/Article/CJFDTOTAL-DZXE201109009.htm
Huang F,Kou D M,Song D,et al.Microscopic Obvervation of the Pyrite Whisker Patterns in Gengzhuang,Shanxi Province,and Its Typomorphic Significance[J].Acta Geologica Sinica,2011,85(9):1486-1492. http://www.cnki.com.cn/Article/CJFDTOTAL-DZXE201109009.htm
[5] 宫丽,马光.黄铁矿的成分标型特征及其在金属矿床中的指示意义[J].地质找矿论丛,2011,26(2):162-166. http://www.cnki.com.cn/Article/CJFDTOTAL-DZZK201102008.htm
Gong L,Ma G.The Characteristic Typomorphic Composition of Pyrite and Its Indicative Meaning to Metal Deposits[J].Contributions to Geology and Mineral Resources Research,2011,26(2):162-166. http://www.cnki.com.cn/Article/CJFDTOTAL-DZZK201102008.htm
[6] 严育通,李胜荣,张娜,等.不同成因类型金矿床成矿期黄铁矿成分成因标型特征[J].黄金,2012,33(3):11-16. http://www.cnki.com.cn/Article/CJFDTOTAL-HJZZ201203004.htm
Yan Y T,Li S R,Zhang N,et al.Composition Typomorphic Characteristics and Statistics Analysis of Metallogenic Pyrite in Gold Deposits of Different Genetic Types[J].Gold,2012,33(3):11-16. http://www.cnki.com.cn/Article/CJFDTOTAL-HJZZ201203004.htm
[7] 谢巧勤,陈天虎,范子良,等.铜陵新桥硫铁矿床中胶状黄铁矿微尺度观察及其成因探讨[J].中国科学(地球科学),2014,44(12):2665-2674. http://www.cnki.com.cn/Article/CJFDTOTAL-JDXK201412006.htm
Xie Q Q,Chen T H,Fan Z L,et al.Morphological Characteristics and Genesis of Colloform Pyrite in Xinqiao Fe-S Deposit,Tongling,Anhui Province[J].Scientia Sinica Terrae,2014,44(12):2665-2674. http://www.cnki.com.cn/Article/CJFDTOTAL-JDXK201412006.htm
[8] 周涛发,张乐骏,袁峰,等.安徽铜陵新桥Cu-Au-S矿床黄铁矿微量元素LA-ICP-MS原位测定及其对矿床成因的制约[J]. 地学前缘,2010,17(2):306-318. http://www.cnki.com.cn/Article/CJFDTOTAL-DXQY201002035.htm
Zhou T F,Zhang L J,Yuan F,et al.LA-ICP-MS in situ Trace Elements Analysis of Pyrite from the Xinqiao Cu-Au-S Deposit in Tongling,Anhui,and Its Constraints on the Ore Genesis[J].Earth Science Frontiers,2010,17(2):306-318. http://www.cnki.com.cn/Article/CJFDTOTAL-DXQY201002035.htm
[9] 袁继海,詹秀春,樊兴涛,等.硫化物矿物中痕量元素的激光剥蚀-电感耦合等离子体质谱微区分析进展[J].岩矿测试,2011,30(2):121-130. http://www.ykcs.ac.cn/ykcs/ch/reader/view_abstract.aspx?file_no=20110202&flag=1
Yuan J H,Zhan X C,Fan X T,et al.Development of Microanalysis of Trace Elements in Sulfide Minerals by Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry[J].Rock and Mineral Analysis,2011,30(2):121-130. http://www.ykcs.ac.cn/ykcs/ch/reader/view_abstract.aspx?file_no=20110202&flag=1
[10] 罗彦,刘勇胜,胡圣虹,等.激光剥蚀电感耦合等离子体质谱测定岩石样品中稀土元素[J].地球科学——中国地质大学学报,2001,26(5):508-512. http://www.cnki.com.cn/Article/CJFDTOTAL-DQKX200105012.htm
Luo Y,Liu Y S,Hu S H,et al.Rare Earth Elements Analysis of Geological Samples by LA-ICP-MS[J].Earth Science-Journal of China University of Geosciences,2001,26(5):508-512. http://www.cnki.com.cn/Article/CJFDTOTAL-DQKX200105012.htm
[11] 肖志斌,柳小明,李正辉,等.激光剥蚀-电感耦合等离子体质谱准确测定锆石中钛的含量[J].岩矿测试,2012,31(2):229-233. http://www.ykcs.ac.cn/ykcs/ch/reader/view_abstract.aspx?file_no=20120206&flag=1
Xiao Z B,Liu X M,Li Z H,et al.Accurate Determination of Ti in Zircon by Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry[J].Rock and Mineral Analysis,2012,31(2):229-233. http://www.ykcs.ac.cn/ykcs/ch/reader/view_abstract.aspx?file_no=20120206&flag=1
[12] 陕亮,许荣科,郑有业,等.北山地区白山堂铜多金属矿区岩浆岩锆石LA-ICP-MS U-Pb年代学及其地质意义[J].中国地质,2013,40(5):1600-1611. http://www.cnki.com.cn/Article/CJFDTOTAL-DIZI201305023.htm
Shan L,Xu R K,Zheng Y Y,et al.Zircon LA-ICP-MS U-Pb Chronology of Magmatic Rock in the Baishantang Copper Polymetallic Deposit of Beishan Area,Northwest China[J].Geology in China,2013,40(5):1600-1611. http://www.cnki.com.cn/Article/CJFDTOTAL-DIZI201305023.htm
[13] 柯于球,张路远,柴辛娜,等.硫化物矿物LA-ICP-MS激光剥蚀元素信号响应[J].高等学校化学学报,2012,33(2):257-262. http://www.cnki.com.cn/Article/CJFDTOTAL-GDXH201202007.htm
Ke Y Q,Zhang L Y,Chai X N,et al.Elemental Signal Response of Sullfise Minerals in LA-ICP-MS Microanalysis[J].Chemical Journal of Chinese Universites,2012,33(2):257-262. http://www.cnki.com.cn/Article/CJFDTOTAL-GDXH201202007.htm
[14] 袁继海,詹秀春,胡明月,等.基于元素对研究激光剥蚀-电感耦合等离子体质谱分析硫化物矿物的基体效应[J]. 光谱学与光谱分析,2015,35(2):512-518. http://www.cnki.com.cn/Article/CJFDTOTAL-GUAN201502052.htm
Yuan J H,Zhan X C,Hu M Y,et al.Characterization of Matrix Effects in Microanalysis of Sulfide Minerals by Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry Based on an Element Pair Method[J]. Spectroscopy and Spectral Analysis,2015,35(2):512-518. http://www.cnki.com.cn/Article/CJFDTOTAL-GUAN201502052.htm
[15] 王彦斌,唐索寒,王进辉,等.安徽铜陵新桥铜金矿床黄铁矿Rb/Sr同位素年龄数据——燕山晚期成矿作用的证据[J].地质论评,2004,50(5):538-541. http://www.cnki.com.cn/Article/CJFDTOTAL-DZLP200405015.htm
Wang Y B,Tang S H,Wang J H,et al.Rb-Sr Dating the Pyrite of the Xinqiao Cu-S-Fe-Au Deposit,Tongling,Anhui Province[J].Geological Review,2004,50(5):538-541. http://www.cnki.com.cn/Article/CJFDTOTAL-DZLP200405015.htm
[16] 梅建明.浙江遂昌治岭头金矿床黄铁矿的化学成分标型研究[J].现代地质,2000,14(1):51-55. http://www.cnki.com.cn/Article/CJFDTOTAL-XDDZ200001010.htm
Mei J M.Chemical Typomorphic Characteristic of Pyrites from Zhilingtou Gold Deposit,Suichang,Zhejiang[J].Geoscience,2000,14(1):51-55. http://www.cnki.com.cn/Article/CJFDTOTAL-XDDZ200001010.htm
[17] 周学武,李胜荣,鲁力,等.辽宁丹东五龙矿区石英脉型金矿床的黄铁矿标型特征研究[J].现代地质,2005,19(2):231-238. http://www.cnki.com.cn/Article/CJFDTOTAL-XDDZ20050200A.htm
Zhou X W,Li S R,Lu L,et al.Study of Pyrite Typomorphic Characteristics of Wulong Quartz-Vein-type Gold Deposit in Dandong, Liaoning Province,China[J].Geoscience,2005,19(2):231-238. http://www.cnki.com.cn/Article/CJFDTOTAL-XDDZ20050200A.htm
[18] 王亚芬.海相火山岩型铜矿床中黄铁矿Co/Ni比值特征及地质意义[J].地质与勘探,1981(8):52-58. http://www.cnki.com.cn/Article/CJFDTOTAL-DZKT198108009.htm
Wang Y F.Pyrite Co/Ni Ratio Characteristics and Geological Significance in Marine Volcanic Type of Copper Deposit[J].Geology and Exploration,1981(8):52-58. http://www.cnki.com.cn/Article/CJFDTOTAL-DZKT198108009.htm
[19] 魏明秀.黄铁矿晶胞参数计算及某些杂质含量分布特征[J].矿物学报,1986,6(3):245-251. http://www.cnki.com.cn/Article/CJFDTOTAL-KWXB198603009.htm
Wei M X.Cell Parameter Equation of Pyrite and Its Genetic Implications[J].Acta Mineralogica Sinica,1986,6(3):245-251. http://www.cnki.com.cn/Article/CJFDTOTAL-KWXB198603009.htm
[20] Clark C,Grguric B,Mumm A S.Genetic Implications of Pyrite Chemistry from the Palaroproterozoic Olary Domain and Overlying Neoproterozoic Adelaidean Sequences,Northeastern South Australia[J].Ore Geology Reviews,2004,25:237-257. doi: 10.1016/j.oregeorev.2004.04.003
[21] 王奎仁编著.地球与宇宙成因矿物学[M].合肥:安徽教育出版社,1989:100-108.
Wang K R.Genetic Mineralogy of Earth and Universe[M].Hefei:Anhui Geological Press,1989:100-108.
[22] 徐国风,邵洁涟.黄铁矿的标型特征及其实际意义[J].地质论评,1980,26(6):541-546. http://www.cnki.com.cn/Article/CJFDTOTAL-DZLP198006015.htm
Xu G F,Shao J L.Typomorphic Characteristics of Pyrite and Its Significance[J].Geological Review,1980,26(6):541-546. http://www.cnki.com.cn/Article/CJFDTOTAL-DZLP198006015.htm
[23] 陕亮,郑有业,许荣科,等.甘肃北山地区白山堂铜矿地质特征及成矿流体研究[J].华南地质与矿产,2012,28(2):149-159. http://www.cnki.com.cn/Article/CJFDTOTAL-HNKC201202009.htm
Shan L,Zheng Y Y,Xu R K,et al.Geological Features and Ore-forming Fluid of Baishantang Copper Deposit in Beishan Area,Gansu Province[J].Geology and Mineral Resources of South China,2012,28(2):149-159. http://www.cnki.com.cn/Article/CJFDTOTAL-HNKC201202009.htm
-
图(3)
表(2)
计量
- 文章访问数: 1659
- PDF下载数: 70
- 施引文献: 0