中山大学曹建劲教授团队发明纳米微粒找矿技术

记者近日获悉，中山大学地球科学与工程学院曹建劲教授团队历经20年的研发，创建形成了完善的纳米微粒找矿技术体系。

该研发结果表明，使用场发射电子探针、纳米离子探针、原子探针等对单一纳米微粒成分做定量分析，结合纳米微粒的形态、结构、聚合关系、超微观生态效应等预测隐伏矿床，能获得更精确的关于隐伏矿体信息。这是中国科研人员发明、中山大学拥有自主知识产权一项找矿技术，也是一项原始创新的国际领先技术，对隐伏矿床找矿具有指导意义。

隐伏矿床找矿技术研究一直是地质学家重要任务之一。曹建劲教授团队经过20年的工作，在30个矿床地表介质中发现3000多个与隐伏矿体有关的纳米金、银、铜、合金微粒以及铜、锂、铌、钽、铟、铷、锗、钼、铅、锌、稀土等元素的硫酸盐、氧化物、氯化物、碳酸盐的纳米微粒。通过对各类型矿床的研究，揭示了从隐伏矿体到地表纳米微粒成分和结构的变化规律。

据悉，曹建劲教授团队研发了在地表土壤气固体、地下水、植物、动物、断层泥等各种介质纳米或接近纳米微粒的采样技术和设备，并研发不同介质纳米微粒的制样和测试技术，分别建立了土壤纳米微粒找矿技术、植物纳米微粒找矿技术、动物纳米微粒找矿技术和水纳米微粒找矿技术，已在14个未知区开展找矿工作，成功预测隐伏矿体。

曹建劲教授团队发明的纳米微粒找矿技术介绍

2003年，曹建劲教授发明将透射电子显微镜载网直接用于野外介质中纳米微粒采样(纳米微粒找矿关键技术之一)，使用透射电子显微镜天然纳米微粒单一微粒分析技术，首次在隐伏矿体上方地表介质中发现纳米金微粒，以及PbSO4、WO3等单一纳米微粒，发明用纳米微粒的种类、大小、形状、结构、化学成分、聚合关系等探测隐伏矿体，创建了纳米微粒找矿技术(Journal of Geochemical Exploration, 2009, 101 (3): 247-253，2007年投稿，2008年在线发表;金属矿山，2009，(2):1-4)。后又在贵州铜厂河铜矿床地表介质中发现自然铜、自然铜铁合金和自然铬铁铜合金纳米微粒，以及含铜的氯化物、氧化物、硫酸盐、氢氧化物纳米微粒(Science China Earth Sciences, 2010, 53: 1647-1654;中国科学: 地球科学, 2011, 41(08): 1109-1115)。在《2008年863计划资源环境技术领域资源高技术论坛》、《2009年第四届全国成矿理论与找矿方法学术讨论会》等学术会议上报告了上述研究成果。

经过20年的工作，在内蒙古东升庙多金属矿床、内蒙古阿右旗卡休他他铁矿床、内蒙古拜仁达坝铅锌银矿床、内蒙古柴胡栏子金矿床、内蒙古维拉斯托银多金属矿床、云南个旧卡房铜矿床、云南会泽大黑山铜矿床、云南永胜得铜矿床、广西清明山铜镍矿床、湖南留书塘铅锌矿床、湖南康家湾多金属矿床、湖南柏坊铜矿床、广东凡口铅锌矿床等30个隐伏矿床地表介质中发现与隐伏矿体有关的含金属纳米微粒，发现的含金属纳米微粒包括纳米金、银、铜、合金等微粒，以及锂、铍、铌、钽、铟、铷、锗、镓、钨、铊、镉、锡、铅、锌、铜、硼、碲、铯、铁、汞、铼、锑、钴、镍、硒、磷、钼、砷、铬、铀、镭、锆、铪、稀土、铂族等元素的氧化物、硫酸盐、氯化物、碳酸盐、氢氧化物纳米微粒和纳米微粒聚合体(图1)，共获得3000多含金属纳米微粒。在所有开展过工作的矿床都在地表介质中发现了与隐伏矿体有关的含金属纳米微粒，证实隐伏矿体地表介质中的含金属纳米微粒是普遍存在的。

已建立各种介质采样、制样、测试，以及微粒特征分析、异常纳米微粒判别、隐伏矿体特征探测等一系列技术，在14个未知区开展找矿工作，成功预测隐伏矿体。目前，曹建劲教授团队共获得8项国家发明专利授权(表1，图1)。

研究结果表明，隐伏矿体纳米微粒是经断裂作用和氧化作用形成，由地下水和上升气流携带到达地表。通过对30个矿床的研究，揭示了各类型矿床从隐伏矿体到地表，纳米微粒在形成和迁移过程中，其成分和结构特征的变化规律，为纳米微粒找矿技术奠定了坚实的基础。

在所研究的地表土壤气固体、地下水、植物、动物、断层泥等介质均发现了大量的隐伏矿体有关的纳米微粒，根据这一发现，分别建立了土壤纳米微粒找矿技术、水纳米微粒找矿技术、植物纳米微粒找矿技术、动物纳米微粒找矿技术。直接观察到含金属纳米微粒造成细胞膜、细胞壁破损、细胞内出现空洞等现象，含金属纳米微粒引起的超微观生物效应也是找矿标志之一。

表1获得授权国家发明专利情况表

图1 《一种利用单一纳米微粒的化学成分数据预测隐伏矿床方法》发明专利证书

发现与隐伏矿体有关纳米微粒有结晶、非晶、混合结构(结晶与非晶同时存在)三种形式，结晶中又可以分出单晶、单一成分多晶、复杂成分多晶等，表明自然流体中的微粒迁移是多形式的。由于纳米微粒性质不同，它们有不同的地球化学行为，它们的吸附、迁移等都有较大的差别，三种形式纳米微粒都有重要的找矿意义。

纳米微粒找矿技术已应用于地震预报、海水入侵探测等其他方面。与隐伏矿体有关的纳米微粒数量可观，潜在生态毒性高，但目前还未引起人们的重视。曹建劲教授团队首次报道与隐伏矿体有关的含铀等纳米微粒对人类健康的潜在威胁。

纳米微粒找矿技术与其它找矿技术有本质的不同。例如，上世纪80年代，瑞典Kristiansson K和Malmqvist L提出地气测量技术，Kristiansson K和Malmqvist L大量的研究表明微气泡能携带含矿物质向上迁移，通过聚苯乙烯薄膜采取这些物质，利用激发X荧光分析等测试手段分析样品的元素含量(全样品分析的综合性元素含量)，通过高的元素含量预测隐伏矿体。因此，曹建劲教授团队发明的纳米微粒找矿技术是前人没有的原始创新找矿技术。该技术获得更丰富和更直接的关于隐伏矿体的信息，能够有效反映隐伏矿体是否存在，以及隐伏矿体的矿物组合、化学成分、矿床类型等信息，应用前景广泛。

上述研究获国家自然科学基金重点项目(内蒙古高原与隐伏金属矿床有关微粒研究，2011年-2014年)、6项面上项目和国家高技术研究发展计划(地气微粒特征和元素含量结合探测隐伏矿床技术研究，2008年-2011年)课题资助。已在《Science China Earth Sciences》、《Chemical Geology》、《Journal of Geochemical Exploration》、《Ore Geology Reviews》等刊物上发表与纳米微粒找矿技术相关论文97篇，部分论文信息(*通信作者)如下：

1 Cao Jianjin*, Hu Ruizhong, Liang Zhirong, Peng Zhuolun. TEM observation of geogas-carried particles from the Changkeng concealed gold deposit, Guangdong Province, South China. Journal of Geochemical Exploration, 2009, 101: 247-253

2 Cao Jianjin*, Liu Chang, Xiong Zhihua, Qin Tingrong. Particles carried by ascending gas flow at the Tongchanghe copper mine, Guizhou Province, China. Science China Earth Sciences, 2010, 53: 1647-1654

3 Hu Guai, Cao Jianjin*. Occurrence and significance of natural ore-related Ag nanoparticles in groundwater systems. Chemical Geology, 2019, 515: 9-21

4 Hu Guai, Cao Jianjin*, Wang Caiyun, Lu Meiqu, Lin Zixia. Study on the characteristics of naturally formed TiO2 nanoparticles in various surficial media from China. Chemical Geology, 2020, 550: 119703

5 Zhang Wanqin, Cao Jianjin*, Luo Xiaoen, Qiu Junwei, Qi Yonghao. Plants emit sulfate‑, phosphate‑ and metal‑containing nanoparticles. Environmental Chemistry Letters, 2023.

6 Liu Rui, Cao Jianjin*, Hu Guai. Revealing a new transport form of natural material by naturally occurring spherical amorphous silica particles in soil aerosol. Chemical Geology, 2021, 559: 119950

7 Lu Meiqu, Cao Jianjin *, Hu Guai, Wang Zeyu, Ma Shaoting. Widespread nearly or nanoscale natural amorphous particles in critical zones from ore deposits[J]. Ore Geology Reviews, 2023, 105454.

8 Cheng Shuting, Cao Jianjin*, Li Yingkui, Hu Guai, Yi Zebang. TEM observations of particles in groundwater and their prospecting significance in the Bofang copper deposit, Hunan, China. Ore Geology Reviews, 2018, 95: 382-400

9 Liu Xiang, Cao Jianjin*, Li Yingkui, Hu Guai, Wang Guoqiang. A study of metal-bearing nanoparticles from the Kangjiawan Pb-Zn deposit and their prospecting significance. Ore Geology Reviews, 2019, 105: 375-386

10 Liu Xiang, Cao Jianjin*, Dang Wanqiang, Lin Zixia, Qiu Junwei. Nanoparticles in groundwater of the Qujia deposit, eastern China: Prospecting significance for deep-seated ore resources. Ore Geology Reviews, 2020, 120: 103417

11 Jiang Tao, Cao Jianjin*, Wu Zhengquan, Wu Yafei, Zeng Jiannian, Wang Zhenghai. A TEM study of particles carried by ascending gas flows from the Bairendaba lead-zinc deposit, Inner Mongolia, China. Ore Geology Reviews, 2019, 105: 18-27

12 Yi Zebang, Cao Jianjin*, Jiang Tao, Wang Zhengyang. Characterization of metal-bearing particles in groundwater from the Weilasituo Zn-Cu-Ag deposit, Inner Mongolia, China: implications for mineral exploration. Ore Geology Reviews, 2020, 117: 103270

13 Hu Guai, Cao Jianjin*, Jiang Tao. Discovery and prospecting significance of metal-bearing nanoparticles within natural invertebrate tissues. Ore Geology Reviews, 2018, 99: 151-165

14 Lu Meiqu, Cao Jianjin*, Liu Xiang, Qiu Junwei. Nanoparticles in various media on surfaces of ore deposits: Study of the more than 1000 m deep concealed Shaling gold deposit. Ore Geology Reviews, 2021, 139: 104466

15 Wang Zeyu, Cao Jianjin*, Qiu Junwei, Liu Xiang. Ore-forming elements and their distribution of nanoparticles in the updraft from the Sanshandao concealed deposit, China. Ore Geology Reviews, 2021, 138: 104371

16 Wang Guoqiang, Cao Jianjin*, Dai Dongle. TEM analysis of nano-or near-nanoparticles in fault gouge from the Kaxiutata iron deposit (CHN) and the implications for ore body exploration. Journal of Geochemical Exploration, 2019, 207: 106390

17 Cao Jianjin*, Cheng Shuting. Characteristics of particles in groundwater and their prospecting significance for the Shijiangshan Pb-Zn-Ag deposit, Inner Mongolia, China. Journal of Geochemical Exploration, 2020, 217: 106592

18 Wang Zhengyang, Cao Jianjin*, Lin Zuxu, Wu Zhengquan. Characteristics of soil particles in the Xiaohulishan deposit, Inner Mongolia, China. Journal of Geochemical Exploration, 2016, 169: 30-42

19 Wei Xiaojun, Cao Jianjin*, Holub F. Robert, Hopke K. Philip, Zhao Shoujin. TEM study of geogas-transported nanoparticles from the Fankou lead–zinc deposit, Guangdong Province, South China. Journal of Geochemical Exploration, 2013, 128: 124-135

20 Luo Songying, Cao Jianjin*, Yan Hongbin, Yi Jie. TEM observations of particles based on sampling in gas and soil at the Dongshengmiao polymetallic pyrite deposit, Inner Mongolia, Northern China. Journal of Geochemical Exploration, 2015, 158: 95-111.

21 Li Yingkui, Cao Jianjin*, Hopke K. Philip, Holub F. Robert, Jiang Tao. The discovery of the metallic particles of groundwater from the Dongshengmiao polymetallic deposit, Inner Mongolia, and their prospecting significance. Journal of Geochemical Exploration, 2016, 161:49-61

22 Luo Xiaoen, Cao Jianjin*. Discovery of nano-sized gold particles in natural plant tissues. Environmental Chemistry Letters, 2018, 16: 1441-1448

23 Cao Jianjin*, Cheng Shuting, Luo Songying, Liu Chang. Study of particles in the ascending gas of ruptures caused by the 2008 Wenchuan earthquake. Applied Geochemistry, 2017, 82: 38-46

24 Peng Zhongze, Cao Jianjin*. Natural uranium‑bearing nanoparticles in surface media. Environmental Chemistry Letters, 2021, 19: 2713-2721

25 Cao Jianjin*, Li Yingkui, Jiang Tao, Hu Guai. Sulfur-containing particles emitted by concealed sulfide ore deposits: an unknown source of sulfur-containing particles in the atmosphere. Atmospheric Chemistry and Physics, 2015, 15: 6959-6969

26 Hu Guai, Cao Jianjin*. Metal-containing nanoparticles derived from concealed metal deposits: an important source of toxic nanoparticles in aquatic environments. Chemosphere, 2019, 224: 726-733

27 Cao Jianjin*, Wei Xiaojun, Ke Hongling, Liu Chang. Study on the particles related to the concealed ore deposits. 25th International Applied Geochemistry Symposium. 2011:61

28 Dai Dongle, Cao Jianjin*, Lai Peixin, Wu Zhengquan. TEM study on particles transported by ascending gas flow in the Kaxiutata iron deposit, Inner Mongolia, North China. Geochemistry: Exploration, Environment, Analysis, 2015, 15: 255-271

29 Cao Jianjin*. Migration mechanisms of gold nanoparticles explored in geogas of the Hetai ore district, southern China. Geochemical Journal, 2011, 45: e9-e13

30 Cao Jianjin*, Hu Xianyong, Jiang Zongtao, Li Hongwei, Zou Xianzhong. Simulation of adsorption of gold nanoparticles carried by gas ascending from the Earth’s interior in alluvial cover of the middle–lower reaches of the Yangtze River. Geofluids, 2010, 10: 438-446

31 Mi Yibo, Cao Jianjin*, Wu Zhengquan, Wang Zhenghai. Transmission electron microscopy analysis on fault gouges from the depths of the Bairendaba polymetallic deposit, Inner Mongolia, China. Journal of Nanoscience and Nanotechnology, 2017, 17: 6549-6557

32 Li Dewei, Cao Jianjin*, Ke Hongling, Liu Chang, Wei Xiaojun. Study of particles from the Kafang copper deposit in Gejiu city, Yunnan. Geochemistry: Exploration, Environment, Analysis, 2017, 17: 367-377

33 Liu Rui, Cao Jianjin*, Deng Yongkang, Wang Guoqiang, Liu Xiang. Formation of nano- or near-nanoparticles via oxidation in the Dabaoshan concealed deposit, Guangdong Province. Arabian Journal of Geosciences, 2020, 13: 1-12

34 Liu Rui, Cao Jianjin*, Luo Songying, Liao Yipeng, Chen Jie. Particulates in the ascending gas caused by the 2013 Ya'an earthquake: A new matter released by earthquake. Geological Journal, 2019, 55: 1216-1226

35 Hu Guai, Cao Jianjin*, Hopke K. Philip, Holub F. Robert. Study of carbon-bearing particles in ascending geogas flows in the dongshengmiao polymetallic pyrite deposit, Inner Mongolia, China. Resource Geology, 2014, 65: 13-26

36 Hu Guai, Cao Jianjin*, Lai Peixin, Hopke K. Philip, Holub F. Robert, Zeng Jiannian, Wang Zhengyang, Wu Zhengquan. Characteristics and geological significance of particles on fractures from the Dongshengmiao polymetallic pyrite deposit, Inner Mongolia, China. Geochemistry: Exploration, Environment, Analysis, 2015, 15:373-381

37 Lu Meiqu, Cao Jianjin*, Wang Zhengyang, Wang Guoqiang. Characteristics of naturally formed nanoparticles in various media and their prospecting significance in Chaihulanzi deposit. Minerals, 2022, 12: 1289

38 Hu Guai, Cao Jianjin*, Jiang Tao, Wang Zhengyang, Yi Zebang. Prospecting application of nanoparticles and nearly nanoscale particles within plant tissues. Resource Geology, 2017, 67:316-329

39 Cao Jianjin*, Jiang Tao, Wu Zhengquan, Li yingkui, Wang Zhengyang, Lin Zuxu. The particles carried by ascending gas in fractures of deep ore deposits. Goldschmidt, 2014: 335

40 Wu Zhengquan, Cao Jianjin*, Yuan Xueling, Luo Songying, Wang Zhengyang. Application of NIR, IR, XRD and XPS in the study of ore deposits. Goldschmidt, 2014: 2743

41 Hu Guai, Cao Jianjin*. The biological accumulation of metallic nanoparticles and its prospecting significance. Goldschmidt, 2018: 1072

42 Cao Jianjin*, Luo Songying, Lai Peixin, Wang Zhengyang, Liao Yipeng, Yi Jie. Research on particles carried by ascending gas flow of earthquake ruptures. Mineralogical Magazine, 2013,77: 820

43 Luo Songying, Cao Jianjin*, Wu Zhengquan. Study of geogas nano-particles of metal deposit in Inner Mongorlia plateau, China. Mineralogical Magazine, 2013,77:1653

44 Cao Jianjin*, Hu Xianyong, Jiang Dan. Transmission electron microscopy study of adsorption of colloidal gold nanoparticles on lepidocrocite and kaolinite. Micro & Nano Letters, 2009, 4: 95-98

45 Cao Jianjin*. Hu Xianyong, Jiang Zongtao, Xiong Zhihua. High resolution TEM studies of small gold particles prepared by the reduction of HAuCl4 with trisodium citric acid. e-Journal of Surface Science and Nanotechnology, 2009, 7: 134-136

46 Cao Jianjin*, Hu Xianyong. Synthesis of gold nanoparticle using halloysites. e-Journal of Surface Science and Nanotechnology, 2009, 7:813-815

47 Cao Jianjin*, Hu Ruizhong, Liu Shen. Simulation test on migration of geogas-carrying gold nanoparticles in slope sediments. Mineral Deposit Research: Meeting the Global Challenge, 2005: 897-900

48 Cao Jianjin*, Hu Ruizhong, Xie Guiqing. Migration of geogas-carrying gold nanoparticles in Quaternary sediments. Goldschmidt Conference Abstracts, 2005: A519

49 曹建劲*, 刘昶, 熊志华, 覃廷荣. 贵州铜厂河铜矿上升气流微粒. 中国科学: 地球科学, 2011, 41(08): 1109-1115

50 曹建劲*. 地气微粒特征和元素含量结合探测隐伏矿床技术. 金属矿山, 2009, 392(02): 1-4

51 曹建劲*, 梁致荣, 刘可星, 张堃, 彭卓伦. 红层风化壳对地气纳米金微粒吸附的模拟实验研究. 自然科学进展, 2004, 14(07): 826-829

52 李映葵, 曹建劲*, 陈杰, 易杰. 广西清明山铜镍硫化物矿床上升气流微粒研究. 岩石学报, 2017, 33(03): 831-842

53 王彩云, 曹建劲*, 戴冬乐. 卡休他他矿床地下水纳米微粒特征及意义. 地球科学, 2018, 43(05): 1650-1662

54 曹建劲*. 隐伏金属矿床上升气流微粒特征、形成及迁移. 地学前缘, 2012, 19(03): 113-119

55 熊志华, 曹建劲*, 刘昶, 刘慎波, 罗文升. 凡口铅锌矿区空气颗粒研究. 金属矿山, 2010, (04): 106-109

56 曹建劲*, 刘昶, 张鹏, 李羿芃, 熊志华. 云南会泽大黑山玄武岩铜矿床地气微粒特征. 金属矿山, 2011, (06): 113-115

57 刘昶, 曹建劲*, 柯红玲. 滇东北永胜得铜矿床地气微粒特征. 化工矿产地质, 2011, 339(04): 201-207

58 袁雪玲, 曹建劲*, 赖佩欣，韦潇君，柯红玲，刘昶. 滇黔交界地区玄武岩铜矿床地气微粒特征. 矿物学报, 2011, 31(增刊): 909

59 袁雪玲, 曹建劲*, 谢方艳, 杨晓洁, 颜鸿斌, 赖佩欣, 王正海, 曾键年. 东升庙硫多金属矿床氧化微粒的XRD, FTIR和XPS分析. 光谱学与光谱分析, 2013, 33(01): 228-232

60 袁雪玲, 曹建劲*, 赖佩欣, 吴政权, 王正海, 曾键年, 吴亚飞. 东升庙硫多金属矿深部氧化带微粒研究. 金属矿山, 2013, (03): 104-107

61 王正阳, 曹建劲*, 吴政权, 林祖旭. 内蒙古东升庙多金属硫化物矿床深部氧化淋滤泥微粒研究. 矿物岩石地球化学通报, 2015, 34(02): 349-353

62 易泽邦, 刘千红, 曹建劲*, 赖佩欣, 彭益军, 张剑, 宾岚. 广州珠江三角洲海水入侵地区地下水微粒的TEM分析及意义. 地质科技情报, 2015, 34(04): 194-199

63 胡乖, 曹建劲*, 易泽邦. 生物体内微粒的发现与找矿. 矿物学报, 2015, 35(增刊): 212

64 曹建劲*, 李映葵, 刘昶, 袁雪玲. 贵州关岭丙坝铜矿床地气微粒特征. 吉林大学学报(地球科学版), 2017, 47(01): 95-105

65党万强, 曹建劲*, 刘昶, 李德伟. 云南小寨铜矿苏家箐矿段地气微粒特征. 矿物岩石, 2018, 38(02): 40-48

66曹建劲*, 胡乖, 姜涛, 王国强, 刘翔. 纳米微粒找矿研究进展. 中国地质学会2019学术年会论文摘要. 2019: 111

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