云南昆阳磷矿黑色页岩微量元素特征及其地质意义
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摘要
昆阳磷矿是我国下寒武统黑色页岩中赋存的最大的磷块岩矿床。为了探讨磷块岩及上覆黑色页岩的源区性质及古海洋的氧化还原环境,本文对梅树村组中谊村段的磷块岩、石岩头段的黑色页岩以及筇竹寺组玉案山段的砂质黑色页岩的地层剖面进行了岩石地球化学研究。发现昆阳剖面磷矿区的下寒武统黑色页岩Th-Zr和Th-Y/Ho比值以及Y-Y/Ho比值与陆源碎屑物质更为接近,石岩头段黑色页岩样品的稀土元素总量平均为174×10-6,与大陆壳稀土总量的平均丰度基本一致。稀土配分模式也十分类似,说明陆源碎屑物质来源比海水自生来源占的比重更大。受陆源碎屑物质的影响,Ni/Co,V/Cr和V/(V+Ni)等氧化还原敏感元素比值并不能很好的指示古海洋的沉积环境。但石岩头段黑色页岩的氧化还原敏感元素相对大陆壳具有一定程度的富集,并且富集程度不强烈,Ce具有轻微的负异常,反映了黑色页岩可能形成于次氧化环境。
The Kunyang phosphorite deposit is the largest phosphorite deposit hosted by Early Cambrian black shale in Yunnan Province,Southwest China. In order to better understand its origin and paleo-redox conditions of phosphorite and overlying black shales,we conduct detailed geochemical study of the Kunyang profile,which spans the phosphorite of Zhongyicun member,black shale of Shiyantou member,and sandy black shale of Yuanshan member. Th-Zr,Th-Y /Ho and Y-Y /Ho plots indicate that metals in black shales were dominantly originated from terrestrial sources. Average ∑REE of the Shiyantou black shales is 174 × 10- 6,similar with that of the continental crust. REE distribution patterns of the Shiyantou black shales are also generally parallel with that of the continental curst. The REE geochemistry indicates that terrestrial origin is greater than the seawater authigenic origin. Due to little proportion of authigenic origin redox sensitive element,Ni /Co,V /Cr and V /( V + Ni) ratios are not suitable to study paleo-redox conditions of seawater. However,slight enrichment of redox sensitive element and weak Ce negative anomalies indicate that the Shiyantou member black shales might formed under suboxic condition.
The Kunyang phosphorite deposit is the largest phosphorite deposit hosted by Early Cambrian black shale in Yunnan Province,Southwest China. In order to better understand its origin and paleo-redox conditions of phosphorite and overlying black shales,we conduct detailed geochemical study of the Kunyang profile,which spans the phosphorite of Zhongyicun member,black shale of Shiyantou member,and sandy black shale of Yuanshan member. Th-Zr,Th-Y /Ho and Y-Y /Ho plots indicate that metals in black shales were dominantly originated from terrestrial sources. Average ∑REE of the Shiyantou black shales is 174 × 10- 6,similar with that of the continental crust. REE distribution patterns of the Shiyantou black shales are also generally parallel with that of the continental curst. The REE geochemistry indicates that terrestrial origin is greater than the seawater authigenic origin. Due to little proportion of authigenic origin redox sensitive element,Ni /Co,V /Cr and V /( V + Ni) ratios are not suitable to study paleo-redox conditions of seawater. However,slight enrichment of redox sensitive element and weak Ce negative anomalies indicate that the Shiyantou member black shales might formed under suboxic condition.
引文
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Pi DH,Liu CQ,Shields-Zhou GA and Jiang SY.2013.Trace and rareearth element geochemistry of black shale and kerogen in the EarlyCambrian Niutitang Formation in Guizhou Province,South China:Constraints for redox environments and origin of metal enrichments.Precambrian Research,225:218-229
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Relvas JMRS,Barriga FJAS,Ferreira A,Noiva PC,Pacheco N andBarrga G.2006.Hydrothermal alteration and mineralization in theNeves-Corvo volcanic-hosted massive sulfide deposit,Portugal.I.Geology,mineralogy,and geochemistry.Economic Geology,101(4):753-790
Rimmer SM.2004.Geochemical paleoredox indicators in DevonianMississippian black shales,central Appalachian basin(USA).Chemical Geology,206(3-4):373-391
Schrder S and Grotzinger JP.2007.Evidence for anoxia at theEdiacaran-Cambrian boundary:The record of redox-sensitive traceelements and rare earth elements in Oman.Journal of the GeologicalSociety,London,164(1):175-187
Shields G and Stille P.2001.Diagenetic constraints on the use of ceriumanormalies as paleoseawater redox proxies:An isotope and REEstudy of Cambrian phosphorites.Chemical Geology,175(1-2):29-48
Steiner M,Zhu MY,Zhao YL and Erdtmann BD.2005.Lower CambrianBurgees Shale-type fossil associations of South China.Palaeogeography,Palaeoclimatology,Palaeoecology,220(1-2):129-152
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Tribovillard N,Algeo TJ,Lyons T and Riboulleau A.2006.Trace metalsas paleoredox and paleoproductivity proxies:An update.ChemicalGeology,232(1-2):12-32
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Xu LG.2011.Early Cambrian black shale and associated polymetallicNi-Mo-PGE-Au mineralization,South China.Ph.D.Dissertation.Claufeld-Zellerfeld:Technical University of Clausthal,1-369
Xu LG,Lehmann B,Mao JW,Qu WJ and Du AD.2011.Re-Os age ofpolymetallic Ni-Mo-PGE-Au mineralization in Early Cambrian blackshales of South China:A reassessment.Economic Geology,106(3):511-522
Xu LG,Lehmann B,Mao JW,Ngler TF,Neubert N and Bttcher ME.2012.Mo isotope and trace element patterns of Early Cambrian blackshales in South China:Constraints on the paleoenvironment.Chemical Geology,318-319:45-59
Xu LG,Lehmann B and Mao JW.2013.Seawater as origin ofpolymetallic Ni-Mo-PGE-Au mineralization in Early Cambrian blackshales of South China:Evidences from Mo isotope,PGE,traceelement and REE geochemistry.Ore Geology Reviews,52:66-84
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Bau M and Dulski P.1996.Distribution of yttrium and rare-earthelements in the Penge and Kuruman iron-formations,TransvaalSupergroup,South Africa.Precambrian Research,79(1-2):37-55
Chen L.2006.Sedimentology and geochemistry of the Early Cambrianblack rock series in the Hunan-Guizhou area,China.Ph.D.Dissertation.Guiyang:Institute of Geochemistry,Chinese Academyof Sciences,1-103(in Chinese)
Compston W,Zhang ZC,Cooper JA,Ma GG and Jenkins RJF.2008.Further SHRIMP geochronology on the Early Cambrian of SouthChina.American Journal of Science,308(4):399-420
Cowie JW.1985.Continuing work on the Precambiran-Cambrianboundary.Episodes,8:93-97
Dill H.1986.Metallogenesis of Early Paleozoic graptolite shales from theGraafenthal Horst(Northern Bavaria-Federal Republic of Germany).Economic Geology,81(4):889-903
Dumoulin JA,Slack JF,Whalen MT and Harris AG.2011.Depositionalsetting and geochemistry of phosphorites and metalliferous blackshales in the Carboniferous-Permian Lisburne Group,northernAlaska.In:Dumoulin JA and Galloway JP(eds.).Studies by theU.S.Geological Survey in Alaska,2008-2009:U.S.GeologicalSurvey Professional Paper 1776-C,64
Elderfield H,Upstill-Goddard R and Sholkovitz ER.1990.The rareearth elements in rivers,estuaries,and coastal seas and theirsignificance to the composition of ocean waters.Geochimica etCosmochimica Acta,54(4):971-991
Fan DL,Yang RY and Huang ZX.1984.The Lower Cambrian blackshales series and the iridium anomaly in South China.Developmentsin Geoscience,27thInternational Geological Congress,Moscow.Beijing:Science Press,215-225
Fan DL,Zhang T and Ye J.2004.Black Shales in China and AssociatedMetalogency.Beijing:Science Publishing House,1-441(inChinese)
Goldberg T,Strauss H,Guo QJ and Liu CQ.2007.Reconstructingmarine redox conditions for the Early Cambrian Yangtze Platform:Evidence from biogenic sulphur and organic carbon isotopes.Palaeogeography,Palaeoclimatology,Palaeoecology,254(1-2):175-193
Han YC,Xia XH,Xiao RG,Wei SS,Yao CM,Yang JH,Tian LS,LianW,Yuan CJ,Hao EH,Liang ZP and Wang BQ.2012.TheChinese Phophate Deposits.Beijing:Geological Publishing House,1-723(in Chinese)
Hatch JR and Leventhal JS.1992.Relationship between inferred redoxpotential of the depositional environment and geochemistry of theUpper Pennsylvanian(Missourian)stark shale member of the Dennislimestone,Wabaunsee country,Kansas,USA.Chemical Geology,99(1-3):65-82
Hu NY,Xia HD,Dai TG,You XJ,Bao ZX and Bao JM.2010.Sedimentary vanadium deposit of Lower Cambrian black rock seriesin western Hunan.Contributions to Geology and Mineral ResourcesResearch,25(4):296-302(In Chinese with English abstract)
Jiang SY,Chen YQ,Ling HF,Yang JH,Feng HZ and Ni P.2006.Trace-and rare-earth element geochemistry and Pb-Pb dating ofblack shales and intercalated Ni-Mo-PGE-Au sulfide ores in LowerCambrian strata,Yangtze Platform,South China.MineraliumDeposita,41(5):453-467
Jiang SY,Zhao HX,Cheng YQ,Yang T,Yang JH and Ling HF.2007.Trace and rare earth element geochemistry of phosphate nodules fromthe Lower Cambrian black shale sequence in the Mufu Mountain ofNanjing,Jiangsu Province,China.Chemical Geology,244(3-4):584-604
Johnson KM and Grimm KA.2001.Opal and organic carbon in laminateddiatomaceous sediments:Saanich Inlet,Santa Barbara Basin and theMiocene Monterey Formation.Marine Geology,174(1-4):159-174
Jones B and Manning DAC.1994.Comparison of geochemical indecesused for the interpretation of palaeoredox conditions in ancientmudstones.Chemical Geology,111(1-4):111-129
Lehmann B,Ngler TF,Holland HD,Wille M,Mao JW,Pan JY,MaDS and Dulski P.2007.Highly metalliferous carbonaceous shaleand Early Cambrian seawater.Geology,35(5):403-406
Lewan MD.1984.Factors controlling the proportionality of vanadium tonickel in crude oils.Geochimica et Cosmochimica Acta,48(11):2231-2238
Liu B,Xu B,Meng XY,Kou XW,He JY,Wei W and Mi H.2007.Study on the chemical index of alteration of Neoproterozoic strata inthe Tarim plate and its implications.Acta Petrologica Sinica,23(7):1664-1670(in Chinese with English abstract)
Ma GL,Beaudoin G,Qi SJ and Li Y.2004.Geology and geochemistry ofthe Changba SEDEX Pb-Zn deposit,Qinling orogenic belt,China.Mineralium Deposita,39(3):380-395
Mao JW,Lehmann B,Du AD,Zhang GD,Ma DS,Wang YT,Zeng MGand Kerrich R.2002.Re-Os dating of polymetallic Ni-Mo-PGE-Aumineralization in Lower Cambrian black shales of South China and itsgeologic significance.Economic Geology,97(5):1051-1061
Mclennan SM.1989.Rare earth elements in sedimentary rocks:Influence of provenance and sedimentary processes.Reviews inMineralogy and Geochemistry,21:169-200
Nesbitt HW and Young GM.1982.Early Proterozoic climates and platemotions inferred from major element chemistry of lutites.Nature,299(5885):715-717
Nozaki Y.1997.A fresh look at element distribution in the North Pacific.Eos(Transactions,American Geophysical Union)
Pang YC,Lin L,Zhu LD,Zhou YH and Ren CY.2011.Features ofCambrian Niutitang Formation in the beidoushan ore district,Weng’an County,Guizhou Province.Geological Bulletin of China,30(8):1245-1250(in Chinese with English abstract)
Pi DH.2007.Geochemistry of Early Cambrian black rock series fromZunyi,Guizhou Province.Ph.D.Dissertation.Guiyang:Instituteof Geochemistry,Chinese Academy of Sciences,1-117(inChinese with English summary)
Pi DH,Liu CQ,Shields-Zhou GA and Jiang SY.2013.Trace and rareearth element geochemistry of black shale and kerogen in the EarlyCambrian Niutitang Formation in Guizhou Province,South China:Constraints for redox environments and origin of metal enrichments.Precambrian Research,225:218-229
Piper DZ.1994.Seawater as the source of minor elements in blackshales,phosphorites and other sedimentary rocks.ChemicalGeology,114(1-2):95-114
Relvas JMRS,Barriga FJAS,Ferreira A,Noiva PC,Pacheco N andBarrga G.2006.Hydrothermal alteration and mineralization in theNeves-Corvo volcanic-hosted massive sulfide deposit,Portugal.I.Geology,mineralogy,and geochemistry.Economic Geology,101(4):753-790
Rimmer SM.2004.Geochemical paleoredox indicators in DevonianMississippian black shales,central Appalachian basin(USA).Chemical Geology,206(3-4):373-391
Schrder S and Grotzinger JP.2007.Evidence for anoxia at theEdiacaran-Cambrian boundary:The record of redox-sensitive traceelements and rare earth elements in Oman.Journal of the GeologicalSociety,London,164(1):175-187
Shields G and Stille P.2001.Diagenetic constraints on the use of ceriumanormalies as paleoseawater redox proxies:An isotope and REEstudy of Cambrian phosphorites.Chemical Geology,175(1-2):29-48
Steiner M,Zhu MY,Zhao YL and Erdtmann BD.2005.Lower CambrianBurgees Shale-type fossil associations of South China.Palaeogeography,Palaeoclimatology,Palaeoecology,220(1-2):129-152
Steiner M,Li GX,Qian Y,Zhu MY and Erdtmann BD.2007.Neoproterozoic to Early Cambrian small selly fossil assemblages and arevised biostratifraphic correlation of the Yangtze Platform(China).Palaeogeography,Palaeoclimatology,Palaeoecology,254(1-2):67-99
Tribovillard N,Algeo TJ,Lyons T and Riboulleau A.2006.Trace metalsas paleoredox and paleoproductivity proxies:An update.ChemicalGeology,232(1-2):12-32
Wang M.2004.Geology,geochemistry and genesis of PGE-polymetallicdeposits,southern China.Ph.D.Dissertation.Guangzhou:Zhongshan University,1-156
Xu LG.2011.Early Cambrian black shale and associated polymetallicNi-Mo-PGE-Au mineralization,South China.Ph.D.Dissertation.Claufeld-Zellerfeld:Technical University of Clausthal,1-369
Xu LG,Lehmann B,Mao JW,Qu WJ and Du AD.2011.Re-Os age ofpolymetallic Ni-Mo-PGE-Au mineralization in Early Cambrian blackshales of South China:A reassessment.Economic Geology,106(3):511-522
Xu LG,Lehmann B,Mao JW,Ngler TF,Neubert N and Bttcher ME.2012.Mo isotope and trace element patterns of Early Cambrian blackshales in South China:Constraints on the paleoenvironment.Chemical Geology,318-319:45-59
Xu LG,Lehmann B and Mao JW.2013.Seawater as origin ofpolymetallic Ni-Mo-PGE-Au mineralization in Early Cambrian blackshales of South China:Evidences from Mo isotope,PGE,traceelement and REE geochemistry.Ore Geology Reviews,52:66-84
Yang F,Xiao RG and Xia XH.2011.Sedimentary environment andgeochemistry of the Kunyang phosphorite deposit in eastern YunnanProvince.Geology and Exploration,47(2):294-303(in Chinesewith English abstract)
Yang QS.2001.Metallogenetic characteristics and prospecting in theblack rock series of East Yuannan and the neighbourhood.YunnanGeology,20(1):59-72(in Chinese with English abstract)
Yang WD,Qi L and Lu XY.1995.Geochemical characteristics andorigin of phosphoric sedimentary formation REE in Early Cambrian inthe eastern Yunnan.Bulletin of Mineralogy Petrology andGeochemistry,12:224-227(in Chinese with English abstract)
Yu BS,Dong HL,Widom E,Chen JQ and Lin CS.2009.Geochemistryof basal Cambrian black shales and cherts from the northern TarimBasin,Northwest China:Implications for depositional setting andtectonic history.Journal of Asian Earth Sciences,34:418-436
Zhu RX,Li XH,Hou XG,Pan YX,Wang F,Deng CL and He HY.2009.SIMS U-Pb zircon age of a tuff layer in the Meishucunsection,Yunnan,Southwest China:Constraint on the age of thePrecambrian-Cambrian boundary.Science in China(Series D),52(9):1385-1392
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