LA-ICPMS原位微区面扫描分析技术及其矿床学应用实例
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摘要
LA-ICPMS原位微区面扫描技术的发展对解析具有包裹体、环带结构的矿物或受多期岩浆/热液活动影响形成的溶蚀再结晶的矿物具有重要的地质意义。黄铁矿作为最普遍的硫化物种类之一,可形成于各种类型矿床中,其微量元素组份记录了矿床形成过程的重要信息。通过LA-ICPMS原位微区面扫描技术获得的黄铁矿晶体内部结构组份信息可用来限定成矿流体的性质、厘定成矿流体的演化规律、示踪成矿物质来源、约束变形变质作用过程中元素的活化和迁移行为,以及约束矿床成因等。本次研究选取了内蒙古二连盆地中巴彦乌拉大型铀矿床、辽宁青城子地区榛子沟铅锌矿、加拿大Pardo砂金矿中的黄铁矿作为研究对象,运用原位微区LA-ICPMS元素面扫描技术揭示其内部组份及结构信息,探索该技术在不同类型矿床中的应用价值。巴彦乌拉大型砂岩型铀矿床中的黄铁矿的内部组构信息显示成矿体系的p H和Eh对硫酸盐还原细菌活动均有影响,并控制与之相关的铀矿化;且成矿体系的p H和Eh受到外界不断供给的地下水的影响,呈振荡性变化。辽宁榛子沟铅锌矿中的黄铁矿的内部组构信息显示矿化过程受到了至少两期流体活动的叠加影响,包括早期同沉积时期的流体以及晚期与燕山期岩浆活动有关的热液流体。加拿大Pardo金矿中黄铁矿的内部组构信息显示矿床中半自形-自形的黄铁矿实际包含碎屑成因的磨圆状核部及后期热液活动形成的增生边;金主要呈浸染状分布在碎屑成因的黄铁矿核部,后期热液活动对金矿化影响微弱。
With the development of two-dimensional trace element mapping by laser-ablation inductively-coupled-plasma mass spectrometry( LA-ICP-MS),it is now possible to reveal in much greater detail any compositional interior textures of the pyrites,thus permitting the investigation of the history of pyrite crystals and providing new insight into the genesis and evolution of mineralisation.Exploiting the advantages of high spatial resolution,low detection limits,and capability of full quantification,LA-ICP-MS elemental mapping is being widely applied to imaging sulphides from various types of deposits. In this study,we applied the LA-ICP-MS elemental mapping technique on pyrites from different types of deposits from China and Canada,for the purpose of monitoring the changes of physio-chemical condition,defining ore genesis,and revealing the distribution patterns of precious metals. The interior compositional textures of pyrites show that the mineralization system of the Bayinwula roll-front U deposit in Inner Mongolia was open and continuously affected by the re-charge of oxidized groundwater,along with a periodic change of p H and Eh that affected the activities of sulphate bacteria and the associated U mineralization. The trace element maps of pyrites from the Zhenzigou Pb-Zn deposit in Liaoning Province indicate that several episodes of fluids were involved and responsible for the mineralisation,namely,an early stage of syn-sedimentary origin and a late hydrothermal mineralisation related to the Yanshanian magmatic activity. The trace element distribution patterns of pyrites from the Palaeoproterozoic placer Au deposit in Canada showed that the subeuhedral-euhedral pyrite,which is a dominant type of pyrite in the conglomerates,is detrital origin and later modified by hydrothermal( or metamorphic) fluids,and Au is mostly associated with the detrital pyrite grains/cores,and disseminated in the porosity on the surface.
With the development of two-dimensional trace element mapping by laser-ablation inductively-coupled-plasma mass spectrometry( LA-ICP-MS),it is now possible to reveal in much greater detail any compositional interior textures of the pyrites,thus permitting the investigation of the history of pyrite crystals and providing new insight into the genesis and evolution of mineralisation.Exploiting the advantages of high spatial resolution,low detection limits,and capability of full quantification,LA-ICP-MS elemental mapping is being widely applied to imaging sulphides from various types of deposits. In this study,we applied the LA-ICP-MS elemental mapping technique on pyrites from different types of deposits from China and Canada,for the purpose of monitoring the changes of physio-chemical condition,defining ore genesis,and revealing the distribution patterns of precious metals. The interior compositional textures of pyrites show that the mineralization system of the Bayinwula roll-front U deposit in Inner Mongolia was open and continuously affected by the re-charge of oxidized groundwater,along with a periodic change of p H and Eh that affected the activities of sulphate bacteria and the associated U mineralization. The trace element maps of pyrites from the Zhenzigou Pb-Zn deposit in Liaoning Province indicate that several episodes of fluids were involved and responsible for the mineralisation,namely,an early stage of syn-sedimentary origin and a late hydrothermal mineralisation related to the Yanshanian magmatic activity. The trace element distribution patterns of pyrites from the Palaeoproterozoic placer Au deposit in Canada showed that the subeuhedral-euhedral pyrite,which is a dominant type of pyrite in the conglomerates,is detrital origin and later modified by hydrothermal( or metamorphic) fluids,and Au is mostly associated with the detrital pyrite grains/cores,and disseminated in the porosity on the surface.
引文
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Bonnetti C,Cuney M,Michels R,Truche L,Malartre F,Liu XD and Yang JX.2015.The multiple roles of sulfate-reducing bacteria and Fe-Ti oxides in the genesis of the Bayinwula roll front-type uranium deposit,Erlian Basin,NE China.Economic Geology,110(4):1059-1081
Bonnetti C,Zhou LL,Riegler T and Brugger J.2018.New visions in the genesis of roll front uranium deposits.Goldschmidt Abstracts,2018:231,https://goldschmidt.info/2018/abstracts/abstractV iew?id=2018001252
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Bullock LA and Parnell J.2017.Selenium and molybdenum enrichment in uranium roll-front deposits of Wyoming and Colorado,USA.Journal of Geochemical Exploration,180:101-112
Chen L,Li XH,Li JW,Hofstra AH,Liu Y and Koenig AE.2015.Extreme variation of sulfur isotopic compositions in pyrite from the Qiuling sediment-hosted gold deposit,West Qinling orogen,central China:An in situ SIMS study with implications for the source of sulfur.Mineralium Deposita,50(6):643-656
Craig JR,Vokes FM and Solberg TN.1998.Pyrite:Physical and chemical textures.Mineralium Deposita,34(1):82-101
de Brodtkorb MK.2009.Precious metal tellurides and other Te-bearing minerals in different paragenesis of Argentina:A review.Revista de la Asociación Geológica Argentina,64(3):365-372
Deditius AP,Utsunomiya S,Renock D,Ewing RC,Ramana CV,Becker U and Kesler SE.2008.A proposed new type of arsenian pyrite:Composition,nanostructure and geological significance.Geochimica et Cosmochimica Acta,72(12):2919-2933
Dong CJ.2012.Geological characteristics of the deposits and analysis of the mineralization system of Qingchengzi Pb-Zn-Au-Ag polymetallic ore field.Ph.D.Dissertation.Beijing:China University of Geosciences(in Chinese with English summary)
Duan XX,Zeng QD,Wang YB,Zhou LL and Chen B.2017.Genesis of the Pb-Zn deposits of the Qingchengzi ore field,eastern Liaoning,China:Constraints from carbonate LA-ICPMS trace element analysis and C-O-S-Pb isotopes.Ore Geology Reviews,89:752-771
Fabbi BP and Moore WJ.1970.Rapid X-ray fluorescence determination of sulfur in mineralized rocks from the Bingham mining district,Utah.Applied Spectroscopy,24(4):426-428
Fan HR,Li XH,Zuo YB,Chen L,Liu S,Hu FF and Feng K.2018.In-situ LA-(MC)-ICPMS and(Nano)SIMS trace elements and sulfur isotope analyses on sulfides and application to confine metallogenic process of ore deposit.Acta Petrologica Sinica,34(12):3479-3496(in Chinese with English abstract)
Flinn JM,Hunter D,Linkous DH,Lanzirotti A,Smith LN,Brightwell Jand Jones BF.2005.Enhanced zinc consumption causes memory deficits and increased brain levels of zinc.Physiology&Behavior,83(5):793-803
Frenzel M,Hirsch T and Gutzmer J.2016.Gallium,germanium,indium,and other trace and minor elements in sphalerite as a function of deposit type:A meta-analysis.Ore Geology Reviews,76:52-78
Gourcerol B,Kontak DJ,Thurston PC and Petrus JA.2018.Results of LA-ICP-MS sulfide mapping from Algoma-type BIF gold systems with implications for the nature of mineralizing fluids,metal sources,and deposit models.Mineralium Deposita,53(6):871-894
Kouhestani H,Ghaderi M,Zaw K,Meffre S and Emami MH.2012.Geological setting and timing of the Chah Zard breccia-hosted epithermal gold-silver deposit in the Tethyan belt of Iran.Mineralium Deposita,47(4):425-440
Large RR,Danyushevsky L,Hollit C,Maslennikov V,Meffre S,Gilbert S,Bull S,Scott R,Emsbo P,Thomas H,Singh B and Foster J.2009.Gold and trace element zonation in pyrite using a laser imaging technique:Implications for the timing of gold in orogenic and Carlinstyle sediment-hosted deposits.Economic Geology,104(5):635-668
Large RR,Mukherjee I,Gregory DD,Steadman JA,Maslennikov VVand Meffre S.2017.Ocean and atmosphere geochemical proxies derived from trace elements in marine pyrite:Implications for ore genesis in sedimentary basins.Economic Geology,112(2):423-450
Li XN and Wang TH.1997.Inversion structures and oil-gas in Erlian Basin.China Offshore Oil and Gas(Geology),11(2):106-110(in Chinese with English abstract)
Liu B,Yang JX,Qin YW,Qiao P and Zhang F.2016.Research on the ore-controlling genetic facies of the sandstone type uranium deposits in the paleo-valley of Saihan Formation of the Erlian Basin.Geology and Exploration,52(6):1037-1047(in Chinese with English abstract)
Liu GP.1999.Isospatial metallogenesis in Qingchengzi ore field,Liaoning.Geological Exploration for Non-Ferrous Metals,8(5):277-282(in Chinese with English abstract)
Liu HX,Kong HQ and Yang YC.2006.Geologic characteristics and genesis of Xiaotongjiapuzi gold deposit,Liaoning Province.Gold,27(5):13-16(in Chinese with English abstract)
Liu WS,Kang SH,Jia LC,Shi QP and Peng C.2013.Characteristics of paleo-valley sandstone-type uranium mineralization in the middle of Erlian Basin.Uranium Geology,29(6):328-335(in Chinese with English abstract)
Liu ZY,Xu XC,Tian YC,Yang DJ,Jiang YZ,Tian SH and Wei M.2007.Relationship between sedimentation-exhalation ore-forming process and gold-silver polymetallic mineralization in Qingchengzi area,Liaoning Province.Mineral Deposits,26(5):563-571(in Chinese with English abstract)
Long DGF,Ulrich T and Kamber BS.2011.Laterally extensive modified placer gold deposits in the Paleoproterozoic Mississagi Formation,Clement and Pardo Townships,Ontario.Canadian Journal of Earth Sciences,48(5):779-792
May TW and Wiedmeyer RH.1998.A table of polyatomic interferences in ICP-MS.Atomic Spectroscopy,19(5):150-155
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Petrus JA,Chew DM,Leybourne MI and Kamber BS.2017.A new approach to laser-ablation inductively-coupled-plasma mass-spectrometry(LA-ICP-MS)using the flexible map interrogation tool‘Monocle’.Chemical Geology,463:76-93
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Ubide T,McK enna CA,Chew DM and Kamber BS.2015.Highresolution LA-ICP-MS trace element mapping of igneous minerals:In search of magma histories.Chemical Geology,409:157-168
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Bonnetti C,Cuney M,Michels R,Truche L,Malartre F,Liu XD and Yang JX.2015.The multiple roles of sulfate-reducing bacteria and Fe-Ti oxides in the genesis of the Bayinwula roll front-type uranium deposit,Erlian Basin,NE China.Economic Geology,110(4):1059-1081
Bonnetti C,Zhou LL,Riegler T and Brugger J.2018.New visions in the genesis of roll front uranium deposits.Goldschmidt Abstracts,2018:231,https://goldschmidt.info/2018/abstracts/abstractV iew?id=2018001252
Bralia A,Sabatini G and Troja F.1979.A revaluation of the Co/Ni ratio in pyrite as geochemical tool in ore genesis problems:Evidences from southern tuscany pyritic deposits.Mineralium Deposita,14(3):353-374
Bullock LA and Parnell J.2017.Selenium and molybdenum enrichment in uranium roll-front deposits of Wyoming and Colorado,USA.Journal of Geochemical Exploration,180:101-112
Chen L,Li XH,Li JW,Hofstra AH,Liu Y and Koenig AE.2015.Extreme variation of sulfur isotopic compositions in pyrite from the Qiuling sediment-hosted gold deposit,West Qinling orogen,central China:An in situ SIMS study with implications for the source of sulfur.Mineralium Deposita,50(6):643-656
Craig JR,Vokes FM and Solberg TN.1998.Pyrite:Physical and chemical textures.Mineralium Deposita,34(1):82-101
de Brodtkorb MK.2009.Precious metal tellurides and other Te-bearing minerals in different paragenesis of Argentina:A review.Revista de la Asociación Geológica Argentina,64(3):365-372
Deditius AP,Utsunomiya S,Renock D,Ewing RC,Ramana CV,Becker U and Kesler SE.2008.A proposed new type of arsenian pyrite:Composition,nanostructure and geological significance.Geochimica et Cosmochimica Acta,72(12):2919-2933
Dong CJ.2012.Geological characteristics of the deposits and analysis of the mineralization system of Qingchengzi Pb-Zn-Au-Ag polymetallic ore field.Ph.D.Dissertation.Beijing:China University of Geosciences(in Chinese with English summary)
Duan XX,Zeng QD,Wang YB,Zhou LL and Chen B.2017.Genesis of the Pb-Zn deposits of the Qingchengzi ore field,eastern Liaoning,China:Constraints from carbonate LA-ICPMS trace element analysis and C-O-S-Pb isotopes.Ore Geology Reviews,89:752-771
Fabbi BP and Moore WJ.1970.Rapid X-ray fluorescence determination of sulfur in mineralized rocks from the Bingham mining district,Utah.Applied Spectroscopy,24(4):426-428
Fan HR,Li XH,Zuo YB,Chen L,Liu S,Hu FF and Feng K.2018.In-situ LA-(MC)-ICPMS and(Nano)SIMS trace elements and sulfur isotope analyses on sulfides and application to confine metallogenic process of ore deposit.Acta Petrologica Sinica,34(12):3479-3496(in Chinese with English abstract)
Flinn JM,Hunter D,Linkous DH,Lanzirotti A,Smith LN,Brightwell Jand Jones BF.2005.Enhanced zinc consumption causes memory deficits and increased brain levels of zinc.Physiology&Behavior,83(5):793-803
Frenzel M,Hirsch T and Gutzmer J.2016.Gallium,germanium,indium,and other trace and minor elements in sphalerite as a function of deposit type:A meta-analysis.Ore Geology Reviews,76:52-78
Gourcerol B,Kontak DJ,Thurston PC and Petrus JA.2018.Results of LA-ICP-MS sulfide mapping from Algoma-type BIF gold systems with implications for the nature of mineralizing fluids,metal sources,and deposit models.Mineralium Deposita,53(6):871-894
Kouhestani H,Ghaderi M,Zaw K,Meffre S and Emami MH.2012.Geological setting and timing of the Chah Zard breccia-hosted epithermal gold-silver deposit in the Tethyan belt of Iran.Mineralium Deposita,47(4):425-440
Large RR,Danyushevsky L,Hollit C,Maslennikov V,Meffre S,Gilbert S,Bull S,Scott R,Emsbo P,Thomas H,Singh B and Foster J.2009.Gold and trace element zonation in pyrite using a laser imaging technique:Implications for the timing of gold in orogenic and Carlinstyle sediment-hosted deposits.Economic Geology,104(5):635-668
Large RR,Mukherjee I,Gregory DD,Steadman JA,Maslennikov VVand Meffre S.2017.Ocean and atmosphere geochemical proxies derived from trace elements in marine pyrite:Implications for ore genesis in sedimentary basins.Economic Geology,112(2):423-450
Li XN and Wang TH.1997.Inversion structures and oil-gas in Erlian Basin.China Offshore Oil and Gas(Geology),11(2):106-110(in Chinese with English abstract)
Liu B,Yang JX,Qin YW,Qiao P and Zhang F.2016.Research on the ore-controlling genetic facies of the sandstone type uranium deposits in the paleo-valley of Saihan Formation of the Erlian Basin.Geology and Exploration,52(6):1037-1047(in Chinese with English abstract)
Liu GP.1999.Isospatial metallogenesis in Qingchengzi ore field,Liaoning.Geological Exploration for Non-Ferrous Metals,8(5):277-282(in Chinese with English abstract)
Liu HX,Kong HQ and Yang YC.2006.Geologic characteristics and genesis of Xiaotongjiapuzi gold deposit,Liaoning Province.Gold,27(5):13-16(in Chinese with English abstract)
Liu WS,Kang SH,Jia LC,Shi QP and Peng C.2013.Characteristics of paleo-valley sandstone-type uranium mineralization in the middle of Erlian Basin.Uranium Geology,29(6):328-335(in Chinese with English abstract)
Liu ZY,Xu XC,Tian YC,Yang DJ,Jiang YZ,Tian SH and Wei M.2007.Relationship between sedimentation-exhalation ore-forming process and gold-silver polymetallic mineralization in Qingchengzi area,Liaoning Province.Mineral Deposits,26(5):563-571(in Chinese with English abstract)
Long DGF,Ulrich T and Kamber BS.2011.Laterally extensive modified placer gold deposits in the Paleoproterozoic Mississagi Formation,Clement and Pardo Townships,Ontario.Canadian Journal of Earth Sciences,48(5):779-792
May TW and Wiedmeyer RH.1998.A table of polyatomic interferences in ICP-MS.Atomic Spectroscopy,19(5):150-155
Meyn HD.1977.Geology of Afton,Scholes,Macbeth and clement townships,districts of Sudbury and Nipissing.Ontario Geological Survey,Report,170:70,https://books.google.ie/books/about/Geology_of_Afton_Scholes_Macbeth_and_Cle.html?id=PRn AtgA ACAAJ&redir_esc=y
Petrus JA,Chew DM,Leybourne MI and Kamber BS.2017.A new approach to laser-ablation inductively-coupled-plasma mass-spectrometry(LA-ICP-MS)using the flexible map interrogation tool‘Monocle’.Chemical Geology,463:76-93
Radtke AS,Heropoulos C,Fabbi BP,Scheiner BJ and Essington M.1972.Data on major and minor elements in host rocks and ores,Carlin gold deposit,Nevada.Economic Geology,67(7):975-978
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