近段时间,中国矿业报报道(首席记者王琼杰):中山大学曹建劲团队发明纳米微粒找矿技术,全文如下:
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 GeochemicalExploration, 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 EarthSciences, 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,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,获得发明专利的申请日期、专利号、名称、发明人、权利人如下:
1、2020.2.18,ZL202010100162.8,一种利用单一纳米微粒的化学成分数据预测隐伏矿床方法,曹建劲、陆美曲、胡乖,中山大学。
2、2010.4.16,ZL201010154422.6,一种地气微粒找矿方法,曹建劲、熊志华、刘昶,中山大学。
3、2014.7.18,ZL201410347067.2,一种水微粒地球化学找矿方法及其应用,曹建劲,中山大学。
4、2014.12.12,ZL201410763148.0,一种利用生物内部纳米微粒寻找隐伏矿床的方法,曹建劲、胡乖中山大学。
5、2016.8.19,ZL201610692141.3,一种利用微粒在生物组织内部引起的超微观异常现象寻找隐伏矿床的方法,曹建劲、胡乖,中山大学。
6、2013.1.4,ZL201310000879.5,一种利用含碳微粒寻找隐伏矿床的方法,曹建劲、赖佩欣中山大学。
7、2013.7.24,ZL201310313191.2,一种微粒预测地震的方法,曹建劲,中山大学。
8、2014.7.18,ZL201410347082.7,一种利用微粒分析判别海水入侵的方法,曹建劲、刘千红、易泽邦、彭益军、赖佩欣、宾兰、张剑,广州市地质调查院、中山大学。
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。
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KristianssonK和Malmqvist L提出地气测量技术,KristianssonK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《ScienceChina Earth Sciences》、《Chemical Geology》、《Journal of Geochemical Exploration》、《OreGeology 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*, HuRuizhong, Liang Zhirong, Peng Zhuolun. TEM observation ofgeogas-carriedparticles from the Changkeng concealed gold deposit, GuangdongProvince, SouthChina. Journal of Geochemical Exploration, 2009, 101: 247-253
2 Cao Jianjin*, LiuChang, Xiong Zhihua, Qin Tingrong. Particles carried byascending gas flow atthe Tongchanghe copper mine, Guizhou Province, China.Science China EarthSciences, 2010, 53: 1647-1654
3 Hu Guai, CaoJianjin*. Occurrence and significance of natural ore-related Agnanoparticlesin groundwater systems. Chemical Geology, 2019, 515: 9-21
4 Hu Guai, CaoJianjin*, Wang Caiyun, Lu Meiqu, Lin Zixia. Study on thecharacteristics ofnaturally formed TiO2 nanoparticles in various surficialmedia fromChina. Chemical Geology, 2020, 550: 119703
5 Zhang Wanqin, CaoJianjin*, Luo Xiaoen, Qiu Junwei, Qi Yonghao. Plants emitsulfate‑, phosphate‑ and metal‑containingnanoparticles. Environmental ChemistryLetters, 2023.
6 Liu Rui, CaoJianjin*, Hu Guai. Revealing a new transport form of naturalmaterial bynaturally occurring spherical amorphous silica particles in soilaerosol.Chemical Geology, 2021, 559: 119950
7 Lu Meiqu, CaoJianjin *, Hu Guai, Wang Zeyu, Ma Shaoting. Widespread nearly ornanoscalenatural amorphous particles in critical zones from ore deposits[J].Ore GeologyReviews, 2023, 105454.
8 Cheng Shuting, CaoJianjin*, Li Yingkui, Hu Guai, Yi Zebang. TEM observationsof particles ingroundwater and their prospecting significance in the Bofangcopper deposit,Hunan, China. Ore Geology Reviews, 2018, 95: 382-400
9 Liu Xiang, CaoJianjin*, Li Yingkui, Hu Guai, Wang Guoqiang. A study ofmetal-bearingnanoparticles from the Kangjiawan Pb-Zn deposit and theirprospectingsignificance. Ore Geology Reviews, 2019, 105: 375-386
10 Liu Xiang, CaoJianjin*, Dang Wanqiang, Lin Zixia, Qiu Junwei. Nanoparticlesin groundwater ofthe Qujia deposit, eastern China: Prospecting significance fordeep-seated oreresources. Ore Geology Reviews, 2020, 120: 103417
11 Jiang Tao, CaoJianjin*, Wu Zhengquan, Wu Yafei, Zeng Jiannian, WangZhenghai. A TEM study ofparticles carried by ascending gas flows from theBairendaba lead-zinc deposit,Inner Mongolia, China. Ore Geology Reviews, 2019,105: 18-27
12Yi Zebang, CaoJianjin*, Jiang Tao, Wang Zhengyang. Characterization ofmetal-bearingparticles in groundwater from the Weilasituo Zn-Cu-Ag deposit,Inner Mongolia,China: implications for mineral exploration. Ore GeologyReviews, 2020, 117:103270
13 Hu Guai, CaoJianjin*, Jiang Tao. Discovery and prospecting significance ofmetal-bearingnanoparticles within natural invertebrate tissues. Ore GeologyReviews, 2018,99: 151-165
14 Lu Meiqu, CaoJianjin*, Liu Xiang, Qiu Junwei. Nanoparticles in various mediaon surfaces ofore deposits: Study of the more than 1000 m deep concealedShaling golddeposit. Ore Geology Reviews, 2021, 139: 104466
15 Wang Zeyu, CaoJianjin*, Qiu Junwei, Liu Xiang. Ore-forming elements andtheir distribution ofnanoparticles in the updraft from the Sanshandao concealeddeposit, China. OreGeology Reviews, 2021, 138: 104371
16 Wang Guoqiang,Cao Jianjin*, Dai Dongle. TEM analysis of nano-ornear-nanoparticles in faultgouge from the Kaxiutata iron deposit (CHN) and theimplications for ore bodyexploration. Journal of Geochemical Exploration, 2019,207: 106390
17 Cao Jianjin*,Cheng Shuting. Characteristics of particles in groundwater andtheirprospecting significance for the Shijiangshan Pb-Zn-Ag deposit, InnerMongolia,China. Journal of Geochemical Exploration, 2020, 217: 106592
18 Wang Zhengyang,Cao Jianjin*, Lin Zuxu, Wu Zhengquan. Characteristics of soilparticles in theXiaohulishan deposit, Inner Mongolia, China. Journal ofGeochemicalExploration, 2016, 169: 30-42
19 Wei Xiaojun, CaoJianjin*, Holub F. Robert, Hopke K. Philip, Zhao Shoujin.TEM study ofgeogas-transported nanoparticles from the Fankou lead–zinc deposit,GuangdongProvince, South China. Journal of Geochemical Exploration, 2013, 128:124-135
20 Luo Songying, CaoJianjin*, Yan Hongbin, Yi Jie. TEM observations ofparticles based on samplingin gas and soil at the Dongshengmiao polymetallicpyrite deposit, Inner Mongolia,Northern China. Journal of GeochemicalExploration, 2015, 158: 95-111.
21 Li Yingkui, CaoJianjin*, Hopke K. Philip, Holub F. Robert, Jiang Tao. Thediscovery of themetallic particles of groundwater from the Dongshengmiaopolymetallic deposit,Inner Mongolia, and their prospecting significance.Journal of GeochemicalExploration, 2016, 161:49-61
22 Luo Xiaoen, CaoJianjin*. Discovery of nano-sized gold particles in naturalplant tissues.Environmental Chemistry Letters, 2018, 16: 1441-1448
23 Cao Jianjin*,Cheng Shuting, Luo Songying, Liu Chang. Study of particles inthe ascending gasof ruptures caused by the 2008 Wenchuan earthquake. AppliedGeochemistry, 2017,82: 38-46
24 Peng Zhongze, Cao Jianjin*. Natural uranium‑bearing nanoparticles in surfacemedia. Environmental Chemistry Letters,2021, 19: 2713-2721
25 Cao Jianjin*, LiYingkui, Jiang Tao, Hu Guai. Sulfur-containing particlesemitted by concealedsulfide ore deposits: an unknown source ofsulfur-containing particles in theatmosphere. Atmospheric Chemistry andPhysics, 2015, 15: 6959-6969
26 Hu Guai, CaoJianjin*. Metal-containing nanoparticles derived from concealedmetal deposits:an important source of toxic nanoparticles in aquaticenvironments.Chemosphere, 2019, 224: 726-733
27 Cao Jianjin*, Wei Xiaojun, KeHongling, Liu Chang. Study on the particlesrelated to the concealed oredeposits. 25th International Applied GeochemistrySymposium. 2011:61
28 Dai Dongle, CaoJianjin*, Lai Peixin, Wu Zhengquan. TEM study on particlestransported byascending 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 geogasof the Hetai oredistrict, southern China. Geochemical Journal, 2011, 45: e9-e13
30 Cao Jianjin*, HuXianyong, Jiang Zongtao, Li Hongwei, Zou Xianzhong.Simulation of adsorption ofgold nanoparticles carried by gas ascending from theEarth’s interior inalluvial cover of the middle–lower reaches of the YangtzeRiver. Geofluids,2010, 10: 438-446
31 Mi Yibo, CaoJianjin*, Wu Zhengquan, Wang Zhenghai. Transmission electronmicroscopyanalysis on fault gouges from the depths of the Bairendabapolymetallicdeposit, Inner Mongolia, China. Journal of Nanoscience andNanotechnology,2017, 17: 6549-6557
32 Li Dewei, CaoJianjin*, Ke Hongling, Liu Chang, Wei Xiaojun. Study ofparticles from theKafang copper deposit in Gejiu city, Yunnan. Geochemistry:Exploration,Environment, Analysis, 2017, 17: 367-377
33 Liu Rui, CaoJianjin*, Deng Yongkang, Wang Guoqiang, Liu Xiang. Formation ofnano- ornear-nanoparticles via oxidation in the Dabaoshan concealed deposit,GuangdongProvince. Arabian Journal of Geosciences, 2020, 13: 1-12
34 LiuRui, Cao Jianjin*, Luo Songying, Liao Yipeng, Chen Jie. Particulates intheascending gas caused by the 2013 Ya'an earthquake: A new matter releasedbyearthquake. Geological Journal, 2019, 55: 1216-1226
35 HuGuai, Cao Jianjin*, Hopke K. Philip, Holub F. Robert. Study ofcarbon-bearingparticles in ascending geogas flows in the dongshengmiaopolymetallic pyritedeposit, Inner Mongolia, China. Resource Geology, 2014, 65:13-26
36 HuGuai, Cao Jianjin*, Lai Peixin, Hopke K. Philip, Holub F. Robert,ZengJiannian, Wang Zhengyang, Wu Zhengquan. Characteristics andgeologicalsignificance of particles on fractures from the Dongshengmiaopolymetallicpyrite deposit, Inner Mongolia, China. Geochemistry: Exploration,Environment,Analysis, 2015, 15:373-381
37 Lu Meiqu, Cao Jianjin*, Wang Zhengyang, WangGuoqiang. Characteristicsofnaturally formed nanoparticles in various media and theirprospectingsignificance in Chaihulanzi deposit. Minerals, 2022, 12: 1289
38 HuGuai, Cao Jianjin*, Jiang Tao, Wang Zhengyang, Yi Zebang.Prospectingapplication of nanoparticles and nearly nanoscale particles withinplanttissues. Resource Geology, 2017, 67:316-329
39 CaoJianjin*, Jiang Tao, Wu Zhengquan, Li yingkui, Wang Zhengyang, Lin Zuxu.Theparticles carried by ascending gas in fractures of deep oredeposits.Goldschmidt, 2014: 335
40 WuZhengquan, Cao Jianjin*, Yuan Xueling, Luo Songying, WangZhengyang.Application of NIR, IR, XRD and XPS in the study of ore deposits.Goldschmidt,2014: 2743
41 HuGuai, Cao Jianjin*. The biological accumulation of metallic nanoparticlesandits prospecting significance. Goldschmidt, 2018: 1072
42 CaoJianjin*, Luo Songying, Lai Peixin, Wang Zhengyang, Liao Yipeng, YiJie.Research on particles carried by ascending gas flow of earthquakeruptures.Mineralogical Magazine, 2013,77: 820
43 LuoSongying, Cao Jianjin*, Wu Zhengquan. Study of geogas nano-particles ofmetaldeposit in Inner Mongorlia plateau, China. Mineralogical Magazine,2013,77:1653
44 CaoJianjin*, Hu Xianyong, Jiang Dan. Transmission electron microscopy studyofadsorption of colloidal gold nanoparticles on lepidocrocite and kaolinite.Micro & NanoLetters, 2009, 4: 95-98
45 CaoJianjin*. Hu Xianyong, Jiang Zongtao, Xiong Zhihua. High resolution TEMstudiesof small gold particles prepared by the reduction of HAuCl4withtrisodium citric acid. e-Journal of Surface Science and Nanotechnology,2009,7: 134-136
46 CaoJianjin*, Hu Xianyong. Synthesis of gold nanoparticle usinghalloysites.e-Journal of Surface Science and Nanotechnology, 2009, 7:813-815
47 CaoJianjin*, Hu Ruizhong, Liu Shen. Simulation test on migrationofgeogas-carrying gold nanoparticles in slope sediments. MineralDepositResearch: Meeting the Global Challenge, 2005: 897-900
48 CaoJianjin*, Hu Ruizhong, Xie Guiqing. Migration of geogas-carryinggoldnanoparticles 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
67 胡乖, 曹建劲*. 隐伏铅锌铜多金属硫化物矿床地表不同介质中纳米微粒特征研究. 中国地质学会2019学术年会论文摘要.2019: 112
68 陆美曲, 曹建劲*, 米一波, 刘翔. 湖南鸭公塘铜铅锌硫多金属矿床地下水纳米微粒特征研究. 金属矿山, 2020, (03): 143-153
69 彭忠泽, 曹建劲*, 何雨璇, 刘翔, 胡乖, 陆美曲. 内蒙古扎木敖包矿床土壤气体纳米微粒特征研究. 金属矿山, 2021, (02): 146-154
70 曹建劲*, 李德伟. 隐伏矿体指示纳米微粒与背景纳米微粒. 第二届中国纳米地球科学学术研讨会暨2016年纳米地球科学国际学术研讨会论文摘要集. 2016
71 胡乖, 曹建劲*. 含金属微粒在生物组织内部引起的超微观异常现象及其找矿应用. 第二届中国纳米地球科学学术研讨会暨2016年纳米地球科学国际学术研讨会论文摘要集, 2016
72 曹建劲*, 蒋宗涛, 熊志华, 杨燕娜, 陈师乐. 硫化物矿床断层微粒的红外光谱分析. 光谱学与光谱分析, 2009, 29(04): 956-959
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 GeochemicalExploration, 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 EarthSciences, 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,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,获得发明专利的申请日期、专利号、名称、发明人、权利人如下:
1、2020.2.18,ZL202010100162.8,一种利用单一纳米微粒的化学成分数据预测隐伏矿床方法,曹建劲、陆美曲、胡乖,中山大学。
2、2010.4.16,ZL201010154422.6,一种地气微粒找矿方法,曹建劲、熊志华、刘昶,中山大学。
3、2014.7.18,ZL201410347067.2,一种水微粒地球化学找矿方法及其应用,曹建劲,中山大学。
4、2014.12.12,ZL201410763148.0,一种利用生物内部纳米微粒寻找隐伏矿床的方法,曹建劲、胡乖中山大学。
5、2016.8.19,ZL201610692141.3,一种利用微粒在生物组织内部引起的超微观异常现象寻找隐伏矿床的方法,曹建劲、胡乖,中山大学。
6、2013.1.4,ZL201310000879.5,一种利用含碳微粒寻找隐伏矿床的方法,曹建劲、赖佩欣中山大学。
7、2013.7.24,ZL201310313191.2,一种微粒预测地震的方法,曹建劲,中山大学。
8、2014.7.18,ZL201410347082.7,一种利用微粒分析判别海水入侵的方法,曹建劲、刘千红、易泽邦、彭益军、赖佩欣、宾兰、张剑,广州市地质调查院、中山大学。
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。
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KristianssonK和Malmqvist L提出地气测量技术,KristianssonK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《ScienceChina Earth Sciences》、《Chemical Geology》、《Journal of Geochemical Exploration》、《OreGeology 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*, HuRuizhong, Liang Zhirong, Peng Zhuolun. TEM observation ofgeogas-carriedparticles from the Changkeng concealed gold deposit, GuangdongProvince, SouthChina. Journal of Geochemical Exploration, 2009, 101: 247-253
2 Cao Jianjin*, LiuChang, Xiong Zhihua, Qin Tingrong. Particles carried byascending gas flow atthe Tongchanghe copper mine, Guizhou Province, China.Science China EarthSciences, 2010, 53: 1647-1654
3 Hu Guai, CaoJianjin*. Occurrence and significance of natural ore-related Agnanoparticlesin groundwater systems. Chemical Geology, 2019, 515: 9-21
4 Hu Guai, CaoJianjin*, Wang Caiyun, Lu Meiqu, Lin Zixia. Study on thecharacteristics ofnaturally formed TiO2 nanoparticles in various surficialmedia fromChina. Chemical Geology, 2020, 550: 119703
5 Zhang Wanqin, CaoJianjin*, Luo Xiaoen, Qiu Junwei, Qi Yonghao. Plants emitsulfate‑, phosphate‑ and metal‑containingnanoparticles. Environmental ChemistryLetters, 2023.
6 Liu Rui, CaoJianjin*, Hu Guai. Revealing a new transport form of naturalmaterial bynaturally occurring spherical amorphous silica particles in soilaerosol.Chemical Geology, 2021, 559: 119950
7 Lu Meiqu, CaoJianjin *, Hu Guai, Wang Zeyu, Ma Shaoting. Widespread nearly ornanoscalenatural amorphous particles in critical zones from ore deposits[J].Ore GeologyReviews, 2023, 105454.
8 Cheng Shuting, CaoJianjin*, Li Yingkui, Hu Guai, Yi Zebang. TEM observationsof particles ingroundwater and their prospecting significance in the Bofangcopper deposit,Hunan, China. Ore Geology Reviews, 2018, 95: 382-400
9 Liu Xiang, CaoJianjin*, Li Yingkui, Hu Guai, Wang Guoqiang. A study ofmetal-bearingnanoparticles from the Kangjiawan Pb-Zn deposit and theirprospectingsignificance. Ore Geology Reviews, 2019, 105: 375-386
10 Liu Xiang, CaoJianjin*, Dang Wanqiang, Lin Zixia, Qiu Junwei. Nanoparticlesin groundwater ofthe Qujia deposit, eastern China: Prospecting significance fordeep-seated oreresources. Ore Geology Reviews, 2020, 120: 103417
11 Jiang Tao, CaoJianjin*, Wu Zhengquan, Wu Yafei, Zeng Jiannian, WangZhenghai. A TEM study ofparticles carried by ascending gas flows from theBairendaba lead-zinc deposit,Inner Mongolia, China. Ore Geology Reviews, 2019,105: 18-27
12Yi Zebang, CaoJianjin*, Jiang Tao, Wang Zhengyang. Characterization ofmetal-bearingparticles in groundwater from the Weilasituo Zn-Cu-Ag deposit,Inner Mongolia,China: implications for mineral exploration. Ore GeologyReviews, 2020, 117:103270
13 Hu Guai, CaoJianjin*, Jiang Tao. Discovery and prospecting significance ofmetal-bearingnanoparticles within natural invertebrate tissues. Ore GeologyReviews, 2018,99: 151-165
14 Lu Meiqu, CaoJianjin*, Liu Xiang, Qiu Junwei. Nanoparticles in various mediaon surfaces ofore deposits: Study of the more than 1000 m deep concealedShaling golddeposit. Ore Geology Reviews, 2021, 139: 104466
15 Wang Zeyu, CaoJianjin*, Qiu Junwei, Liu Xiang. Ore-forming elements andtheir distribution ofnanoparticles in the updraft from the Sanshandao concealeddeposit, China. OreGeology Reviews, 2021, 138: 104371
16 Wang Guoqiang,Cao Jianjin*, Dai Dongle. TEM analysis of nano-ornear-nanoparticles in faultgouge from the Kaxiutata iron deposit (CHN) and theimplications for ore bodyexploration. Journal of Geochemical Exploration, 2019,207: 106390
17 Cao Jianjin*,Cheng Shuting. Characteristics of particles in groundwater andtheirprospecting significance for the Shijiangshan Pb-Zn-Ag deposit, InnerMongolia,China. Journal of Geochemical Exploration, 2020, 217: 106592
18 Wang Zhengyang,Cao Jianjin*, Lin Zuxu, Wu Zhengquan. Characteristics of soilparticles in theXiaohulishan deposit, Inner Mongolia, China. Journal ofGeochemicalExploration, 2016, 169: 30-42
19 Wei Xiaojun, CaoJianjin*, Holub F. Robert, Hopke K. Philip, Zhao Shoujin.TEM study ofgeogas-transported nanoparticles from the Fankou lead–zinc deposit,GuangdongProvince, South China. Journal of Geochemical Exploration, 2013, 128:124-135
20 Luo Songying, CaoJianjin*, Yan Hongbin, Yi Jie. TEM observations ofparticles based on samplingin gas and soil at the Dongshengmiao polymetallicpyrite deposit, Inner Mongolia,Northern China. Journal of GeochemicalExploration, 2015, 158: 95-111.
21 Li Yingkui, CaoJianjin*, Hopke K. Philip, Holub F. Robert, Jiang Tao. Thediscovery of themetallic particles of groundwater from the Dongshengmiaopolymetallic deposit,Inner Mongolia, and their prospecting significance.Journal of GeochemicalExploration, 2016, 161:49-61
22 Luo Xiaoen, CaoJianjin*. Discovery of nano-sized gold particles in naturalplant tissues.Environmental Chemistry Letters, 2018, 16: 1441-1448
23 Cao Jianjin*,Cheng Shuting, Luo Songying, Liu Chang. Study of particles inthe ascending gasof ruptures caused by the 2008 Wenchuan earthquake. AppliedGeochemistry, 2017,82: 38-46
24 Peng Zhongze, Cao Jianjin*. Natural uranium‑bearing nanoparticles in surfacemedia. Environmental Chemistry Letters,2021, 19: 2713-2721
25 Cao Jianjin*, LiYingkui, Jiang Tao, Hu Guai. Sulfur-containing particlesemitted by concealedsulfide ore deposits: an unknown source ofsulfur-containing particles in theatmosphere. Atmospheric Chemistry andPhysics, 2015, 15: 6959-6969
26 Hu Guai, CaoJianjin*. Metal-containing nanoparticles derived from concealedmetal deposits:an important source of toxic nanoparticles in aquaticenvironments.Chemosphere, 2019, 224: 726-733
27 Cao Jianjin*, Wei Xiaojun, KeHongling, Liu Chang. Study on the particlesrelated to the concealed oredeposits. 25th International Applied GeochemistrySymposium. 2011:61
28 Dai Dongle, CaoJianjin*, Lai Peixin, Wu Zhengquan. TEM study on particlestransported byascending 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 geogasof the Hetai oredistrict, southern China. Geochemical Journal, 2011, 45: e9-e13
30 Cao Jianjin*, HuXianyong, Jiang Zongtao, Li Hongwei, Zou Xianzhong.Simulation of adsorption ofgold nanoparticles carried by gas ascending from theEarth’s interior inalluvial cover of the middle–lower reaches of the YangtzeRiver. Geofluids,2010, 10: 438-446
31 Mi Yibo, CaoJianjin*, Wu Zhengquan, Wang Zhenghai. Transmission electronmicroscopyanalysis on fault gouges from the depths of the Bairendabapolymetallicdeposit, Inner Mongolia, China. Journal of Nanoscience andNanotechnology,2017, 17: 6549-6557
32 Li Dewei, CaoJianjin*, Ke Hongling, Liu Chang, Wei Xiaojun. Study ofparticles from theKafang copper deposit in Gejiu city, Yunnan. Geochemistry:Exploration,Environment, Analysis, 2017, 17: 367-377
33 Liu Rui, CaoJianjin*, Deng Yongkang, Wang Guoqiang, Liu Xiang. Formation ofnano- ornear-nanoparticles via oxidation in the Dabaoshan concealed deposit,GuangdongProvince. Arabian Journal of Geosciences, 2020, 13: 1-12
34 LiuRui, Cao Jianjin*, Luo Songying, Liao Yipeng, Chen Jie. Particulates intheascending gas caused by the 2013 Ya'an earthquake: A new matter releasedbyearthquake. Geological Journal, 2019, 55: 1216-1226
35 HuGuai, Cao Jianjin*, Hopke K. Philip, Holub F. Robert. Study ofcarbon-bearingparticles in ascending geogas flows in the dongshengmiaopolymetallic pyritedeposit, Inner Mongolia, China. Resource Geology, 2014, 65:13-26
36 HuGuai, Cao Jianjin*, Lai Peixin, Hopke K. Philip, Holub F. Robert,ZengJiannian, Wang Zhengyang, Wu Zhengquan. Characteristics andgeologicalsignificance of particles on fractures from the Dongshengmiaopolymetallicpyrite deposit, Inner Mongolia, China. Geochemistry: Exploration,Environment,Analysis, 2015, 15:373-381
37 Lu Meiqu, Cao Jianjin*, Wang Zhengyang, WangGuoqiang. Characteristicsofnaturally formed nanoparticles in various media and theirprospectingsignificance in Chaihulanzi deposit. Minerals, 2022, 12: 1289
38 HuGuai, Cao Jianjin*, Jiang Tao, Wang Zhengyang, Yi Zebang.Prospectingapplication of nanoparticles and nearly nanoscale particles withinplanttissues. Resource Geology, 2017, 67:316-329
39 CaoJianjin*, Jiang Tao, Wu Zhengquan, Li yingkui, Wang Zhengyang, Lin Zuxu.Theparticles carried by ascending gas in fractures of deep oredeposits.Goldschmidt, 2014: 335
40 WuZhengquan, Cao Jianjin*, Yuan Xueling, Luo Songying, WangZhengyang.Application of NIR, IR, XRD and XPS in the study of ore deposits.Goldschmidt,2014: 2743
41 HuGuai, Cao Jianjin*. The biological accumulation of metallic nanoparticlesandits prospecting significance. Goldschmidt, 2018: 1072
42 CaoJianjin*, Luo Songying, Lai Peixin, Wang Zhengyang, Liao Yipeng, YiJie.Research on particles carried by ascending gas flow of earthquakeruptures.Mineralogical Magazine, 2013,77: 820
43 LuoSongying, Cao Jianjin*, Wu Zhengquan. Study of geogas nano-particles ofmetaldeposit in Inner Mongorlia plateau, China. Mineralogical Magazine,2013,77:1653
44 CaoJianjin*, Hu Xianyong, Jiang Dan. Transmission electron microscopy studyofadsorption of colloidal gold nanoparticles on lepidocrocite and kaolinite.Micro & NanoLetters, 2009, 4: 95-98
45 CaoJianjin*. Hu Xianyong, Jiang Zongtao, Xiong Zhihua. High resolution TEMstudiesof small gold particles prepared by the reduction of HAuCl4withtrisodium citric acid. e-Journal of Surface Science and Nanotechnology,2009,7: 134-136
46 CaoJianjin*, Hu Xianyong. Synthesis of gold nanoparticle usinghalloysites.e-Journal of Surface Science and Nanotechnology, 2009, 7:813-815
47 CaoJianjin*, Hu Ruizhong, Liu Shen. Simulation test on migrationofgeogas-carrying gold nanoparticles in slope sediments. MineralDepositResearch: Meeting the Global Challenge, 2005: 897-900
48 CaoJianjin*, Hu Ruizhong, Xie Guiqing. Migration of geogas-carryinggoldnanoparticles 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
67 胡乖, 曹建劲*. 隐伏铅锌铜多金属硫化物矿床地表不同介质中纳米微粒特征研究. 中国地质学会2019学术年会论文摘要.2019: 112
68 陆美曲, 曹建劲*, 米一波, 刘翔. 湖南鸭公塘铜铅锌硫多金属矿床地下水纳米微粒特征研究. 金属矿山, 2020, (03): 143-153
69 彭忠泽, 曹建劲*, 何雨璇, 刘翔, 胡乖, 陆美曲. 内蒙古扎木敖包矿床土壤气体纳米微粒特征研究. 金属矿山, 2021, (02): 146-154
70 曹建劲*, 李德伟. 隐伏矿体指示纳米微粒与背景纳米微粒. 第二届中国纳米地球科学学术研讨会暨2016年纳米地球科学国际学术研讨会论文摘要集. 2016
71 胡乖, 曹建劲*. 含金属微粒在生物组织内部引起的超微观异常现象及其找矿应用. 第二届中国纳米地球科学学术研讨会暨2016年纳米地球科学国际学术研讨会论文摘要集, 2016
72 曹建劲*, 蒋宗涛, 熊志华, 杨燕娜, 陈师乐. 硫化物矿床断层微粒的红外光谱分析. 光谱学与光谱分析, 2009, 29(04): 956-959