黔西南板其卡林型金矿床方解石REE、Fe、Mn元素特征及其对找矿的指示意义
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摘要
板其金矿床是黔西南卡林型金矿矿集区内的重要组成部分,是中国发现的第一个卡林型金矿床。方解石是其最主要的脉石矿物,按形成时间可分为成矿前、主成矿期、成矿晚期、成矿期后四种类型。各类型方解石无论野外产状、物性标型特征还是微量元素地球化学特征均不一致。四种类型方解石相比较,成矿前方解石稀土元素总量最高(ΣREE=29.70～40.10μg/g),最富集轻稀土元素(LREE/HREE=1.96～3.03),具有最大正Eu异常(δEu=3.83～5.02),无明显Ce异常(δCe=1.02～1.05);主成矿期方解石稀土元素总量相对较低(ΣREE=10.76～15.53μg/g),最富集重稀土元素(LREE/HREE=0.11～0.23),Eu异常(δEu=0.73～1.20)与Ce异常(δCe=0.88～1.25)均不明显;成矿晚期方解石稀土元素总量最低(ΣREE=2.82～4.34μg/g),与主成矿期方解石相似,具有重稀土元素富集特征(LREE/HREE=0.26～0.86),具有弱的负Eu异常(δEu=0.67～0.83)及负Ce异常(δCe=0.55～0.81);成矿期后方解石稀土元素总量相对较低(ΣREE=6.92～10.91μg/g),轻稀土元素富集(LREE/HREE=1.83～2.34),弱负Eu异常(δEu=0.72～0.74)与中等负Ce异常(δCe=0.41～0.50)。此外,成矿期方解石Fe、Mn元素含量明显高于非成矿期方解石,而且方解石Fe+Mn含量与LREE/HREE比值具有明显负相关关系,说明板其金矿床方解石富集重稀土元素与其所含的Fe、Mn元素有关。对方解石各种标型特征的研究,将为滇黔桂卡林型金矿找矿勘查提供重要手段。
The Banqi gold deposit is one of the important Carlin-type gold deposits in the southwestern Guizhou Carlin-type gold district, and it is the first deposit of the type found in China. As the major gangue mineral in this deposit, calcite can be divided into four types based on their formation time: pre-mineralization, main metallogenic epoch, late stage of mineralization, and post-mineralization. All types of calcites have distinct features such as field occurrence, physical typomorphic characteristics and trace elements characteristics. The pre-mineralization calcites have the highest REE contents(∑REE=29.70–40.10 μg/g), which are characterized by the most enriched LREE(LREE/HREE=1.96–3.03), a distinct positive Eu anomalies(δEu=3.83–5.02), and almost no Ce anomalies(δCe=1.02–1.05). The calcites of the main metallogenic epoch have relatively low REE contents(∑REE=10.76–15.53 μg/g), and are characterized by the most enriched HREE(LREE/HREE=0.11–0.23), almost no Eu(δEu=0.73–1.20) and Ce anomalies(δCe=0.88–1.25). The calcites of the late stage of mineralization have the lowest REE contents(∑REE=2.82–4.34 μg/g), and are characterized by enriched HREE(LREE/HREE=0.26–0.86), weakly negative Eu(δEu=0.67–0.83) and Ce anomalies(δCe=0.55–0.81), which are similar to those of the calcites of the main metallogenic epoch. The post-mineralization calcites have relatively low REE contents(∑REE=6.92–10.91 μg/g), characterized by enriched LREE(LREE/HREE=1.83–2.34), weakly negative Eu anomalies(δEu=0.72–0.74) and moderately negative Ce anomalies(δCe=0.41–0.50). In addition, the Fe and Mn contents of ore-forming stage calcites are obviously higher than that of the calcites unrelated to mineralization, and negatively correlated with LREE/HREE ratio, which illustrates that the HREE concentrations of calcites are controlled by the incorporation of Fe and Mn. Thus, it will provide an important exploration indicator for the Yunnan-Guizhou-Guangxi Carlin-type gold deposits through the study of typomorphic characteristics of calcite.
The Banqi gold deposit is one of the important Carlin-type gold deposits in the southwestern Guizhou Carlin-type gold district, and it is the first deposit of the type found in China. As the major gangue mineral in this deposit, calcite can be divided into four types based on their formation time: pre-mineralization, main metallogenic epoch, late stage of mineralization, and post-mineralization. All types of calcites have distinct features such as field occurrence, physical typomorphic characteristics and trace elements characteristics. The pre-mineralization calcites have the highest REE contents(∑REE=29.70–40.10 μg/g), which are characterized by the most enriched LREE(LREE/HREE=1.96–3.03), a distinct positive Eu anomalies(δEu=3.83–5.02), and almost no Ce anomalies(δCe=1.02–1.05). The calcites of the main metallogenic epoch have relatively low REE contents(∑REE=10.76–15.53 μg/g), and are characterized by the most enriched HREE(LREE/HREE=0.11–0.23), almost no Eu(δEu=0.73–1.20) and Ce anomalies(δCe=0.88–1.25). The calcites of the late stage of mineralization have the lowest REE contents(∑REE=2.82–4.34 μg/g), and are characterized by enriched HREE(LREE/HREE=0.26–0.86), weakly negative Eu(δEu=0.67–0.83) and Ce anomalies(δCe=0.55–0.81), which are similar to those of the calcites of the main metallogenic epoch. The post-mineralization calcites have relatively low REE contents(∑REE=6.92–10.91 μg/g), characterized by enriched LREE(LREE/HREE=1.83–2.34), weakly negative Eu anomalies(δEu=0.72–0.74) and moderately negative Ce anomalies(δCe=0.41–0.50). In addition, the Fe and Mn contents of ore-forming stage calcites are obviously higher than that of the calcites unrelated to mineralization, and negatively correlated with LREE/HREE ratio, which illustrates that the HREE concentrations of calcites are controlled by the incorporation of Fe and Mn. Thus, it will provide an important exploration indicator for the Yunnan-Guizhou-Guangxi Carlin-type gold deposits through the study of typomorphic characteristics of calcite.
引文
陈振强.1996.锡铁山铅锌矿中石英、方解石的热发光研究.矿产与地质,10(56):412-416.
成欣怡,林锦富.2009.方解石矿物学与微量元素地球化学研究现状.第三届华南青年地学学术研讨会论文集.160-164.
邓红,黄智龙,肖宪国,丁伟.2014.贵州半坡锑矿床方解石稀土元素地球化学研究.矿物学报,34(2):208-216.
黄智龙,陈进,韩润生,李文博,高德荣,赵德顺,刘丛强.2001.云南会泽铅锌矿床脉石矿物方解石REE地球化学.矿物学报,21(4):659-666.
彭建堂,胡瑞忠,漆亮,赵军红,符亚洲.2004.锡矿山热液方解石的REE分配模式及其制约因素.地质论评,50(1):25-32.
涂光炽.2002.我国西南地区两个别具一格的成矿带(域).矿物岩石地球化学通报,21(1):1-2.
王登红,李超,陈郑辉,王成辉,黄凡,屈文俊.2012.辉钼矿在矿床学研究中的新用途(I):稀土元素示踪.吉林大学学报(自然科学版),42(6):1647-1655.
王加昇,温汉捷,石少华.2010.湘黔汞矿带脉石矿物方解石稀土元素、碳氧同位素特征及其指示意义.矿物学报,30(2):185-193.
王泽鹏,夏勇,宋谢炎,游彬,郑新华,汪小勇.2012.太平洞-紫木凼金矿区同位素和稀土元素特征及成矿物质来源探讨.矿物学报,32(1):93-100.
魏爱英.2011.滇东北毛坪铅锌矿床Ⅰ号矿群蚀变-矿化分带模式研究.昆明:昆明理工大学硕士论文,1-127.
谢卓君,夏勇,闫宝文,王泽鹏,谭亲平,伍守荣,范二川.2014.贵州省三都-丹寨成矿带中卡林型金矿地球化学特征及成矿物质来源初探.矿物岩石地球化学通报,33(3):326-333.
张鸿翔.2009.我国特色成矿系统的研究进展与重点关注的科学问题.地球科学进展,24(5):563-570.
张瑜,夏勇,王泽鹏,闫宝文,付芝康,陈明.2010.贵州簸箕田金矿单矿物稀土元素和同位素地球化学特征.地学前缘,17(2):385-395.
朱赖民,段启杉.1998.贵州西南部板其卡林型金矿床成矿过程分析.黄金,19(4):8-12.
邹明亮,王琦,李剑,梁永东,李冉.2012.多金属矿床中方解石的地球化学特征反映的成矿流体性质.地质找矿论丛,27(4):391-398.
Almqvist B S G,Herwegh M,Schmidt V,Pettke T and Hirt AM.2010.Magnetic susceptibility as a tool to study deformed calcite with variable impurity content.Geochemistry Geophysics Geosystems,11:1-15.
Alt J C.1988.The chemistry and sulfur isotope composition of massive sulfide and associated deposits on Green Seamount,eastern Pacific.Economic Geology,83(5):1026-1033.
Bau M.1991.Rare-earth element mobility during hydrothermal and metamorphic fluid-rock interaction and the significance of the oxidation state of europium.Chemical Geology,93(3-4):219-230.
Bau M,Koschinsky A,Dulski P and Hein J R.1996.Comparison of the partitioning behaviours of yttrium,rare earth elements,and titanium between hydrogenetic marine ferromanganese crusts and seawater.Geochimica et Cosmochimica Acta,60(10):1709-1725.
Bau M and M?ller P.1992.Rare earth element fractionation in metamorphogenic hydrothermal calcite,magnesite and siderite.Mineralogy and Petrology,45(3-4):231-246.
Brugger J and Meisser N.2006.Manganese-rich assemblages in the Barrhorn Unit,Turtmanntal,Central Alps,Switzerland.The Canadian Mineralogist,44(1):229-248.
Chesley J T,Halliday A N and Scrivener R C.1991.Samariumneodymium direct dating of fluorite mineralization.Science,252(2008):949-951.
Freund D,Rybacki E and Dresen G.2001.Effect of impurities on grain growth in synthetic calcite aggregates,Physics and Chemistry of Minerals,28:737-745.
Freund D,Wang Z,Rybacki E and Dresen G.2004.Hightemperature creep of synthetic calcite aggregates:Influence of Mn content.Earth and Planetary Science Letters,226:433-448.
Graf J L.1984.Effects of Mississippi Valley-type mineralization on REE patterns of carbonate rocks and minerals,viburnum trend,Southeast Missouri.Journal of Geology,92(3):307-324.
Hu R Z,Su W C,Bi X W,Tu G C and Hofstra A H.2002.Geology and geochemistry of Carlin-type Au deposits in China.Mineralium Deposita,37:378-392.
Johannesson K H,Lyons W B,Yelken M A,Gaudette H Eand Stetzenbach K J.1996.Geochemistry of rare earth elements in hypersaline and dilute acidic natural terrestrial waters:Complexation behaviour and middle rare earth element enrichment.Chemical Geology,133(1-4):124-144.
Kato Y,Fujinaga K,Nozaki T,Osawa H,Nakamura K and Ono R.2005.Rare earth,major and trace elements in the Kunimiyama ferromanganese deposit in the northern Chichibu belt,Central Shikoku,Japan.Resource Geology,55(4):291-299.
Morgan J W and Wandless G A.1980.Rare earth element in some hydrothermal minerals:Evidence for crystallographic control.Geochimica et Cosmochimica Acta,44(7):973-980.
Palmer M R.1985.Rare earth elements in foraminifera tests.Earth and Planetary Science Letters,73(2-4):285-298.
Palmer M R and Elderfield H.1986.Rare earth elements and neodymium isotopes in ferromanganese oxide coatings of Cenozoic foraminifera from the Atlantic Ocean.Geochimica et Cosmochimica Acta,50(3):409-417.
Peng J T,Hu R Z and Burnard P G.2003.Samariumneodymium isotope systematics of hydrothermal calcites from the Xikuangshan antimony deposit(Hunan,China):The potential of calcite as a geochronometer.Chemical Geology,200(1):129-136.
Sch?nenberger J,K?hler J and Markl G.2008.REE systematics of fluorides,calcite and siderite in peralkaline plutonic rocks from the Gardar Province,South Greenland.Chemical Geology,247(1-2):16-35.
Shuang Y,Bi X W,Hu R Z,Peng J T,Li H,Li D H and Zhu C S.2010.REE,Mn,Fe,Mg and C,O isotopic geochemistry of calcites from Furong tin deposit,South China:Evidence for the genesis of the hydrothermal ore-forming fluids.Resource Geology,60(1):18-34.
Su W C,Hu R Z,Xia B,Xia Y and Liu Y P.2009.Calcite Sm-Nd isochron age of the Shuiyindong Carlin-type gold deposit,Guizhou,China.Chemical Geology,258(3-4):269-274.
Su W C,Xia B,Zhang H T,Zhang X C and Hu R Z.2008.Visible gold in arsenian pyrite at the Shuiyindong Carlin-type gold deposit,Guizhou,China:Implications for the environment and processes of ore formation.Ore Geology Reviews,33(3):667-679.
Su W C,Zhang H T,Hu R Z,Ge X,Xia B,Chen Y Y and Zhu C.2012.Mineralogy and geochemistry of gold-bearing arsenian pyrite from the Shuiyindong Carlin-type gold deposit,Guizhou,China:Implications for gold depositional processes.Mineralium Deposita,47(6):653-662.
Subías I and Fernández-Nieto C.1995.Hydrothermal events in the Valle de Tena(Spanish Western Pyrenees)as evidenced by fluid inclusions and trace-element distribution from fluorite deposits.Chemical Geology,124(3-4):267-282.
Sun S S and Mc Donough W F.1989.Chemical and isotopic systematic of oceanic basalts:Implication for the mantle composition and process.Geological Society of London Special Publication,42(1):313-345.
Uysal T,Zhao J X,Golding S D,Lawrence M G,Glikson Mand Collerson K D.2007.Sm-Nd dating and rare earth element tracing of calcite:Implications for fluid-flow events in the Bowen Basin,Australia.Chemical Geology,238(1-2):63-71.
Wang J S,Wen H J,Fan H F and Zhu J J.2012.Sm-Nd geochronology,REE geochemistry and C and O isotope characteristics of calcites and stibnites from the Banian antimony deposit,Guizhou Province,China.Geochemical Journal,46(5):393-407.
Wildeman T R.1970.The distribution of Mn2+in some carbonates by electron paramagnetic resonance.Chemical Geology,5:167-177.
Yan B W,Xia Y,Wang Z P,Tan Q P,Wu S R and Fan E C.2012.Geochemical characteristics and metallogenesis of Carlin-type gold deposits in the Sandu-Danzhai metallogenic zone,Guizhou Province,China.Chinese Journal of Geochemistry,31(3):209-220.
成欣怡,林锦富.2009.方解石矿物学与微量元素地球化学研究现状.第三届华南青年地学学术研讨会论文集.160-164.
邓红,黄智龙,肖宪国,丁伟.2014.贵州半坡锑矿床方解石稀土元素地球化学研究.矿物学报,34(2):208-216.
黄智龙,陈进,韩润生,李文博,高德荣,赵德顺,刘丛强.2001.云南会泽铅锌矿床脉石矿物方解石REE地球化学.矿物学报,21(4):659-666.
彭建堂,胡瑞忠,漆亮,赵军红,符亚洲.2004.锡矿山热液方解石的REE分配模式及其制约因素.地质论评,50(1):25-32.
涂光炽.2002.我国西南地区两个别具一格的成矿带(域).矿物岩石地球化学通报,21(1):1-2.
王登红,李超,陈郑辉,王成辉,黄凡,屈文俊.2012.辉钼矿在矿床学研究中的新用途(I):稀土元素示踪.吉林大学学报(自然科学版),42(6):1647-1655.
王加昇,温汉捷,石少华.2010.湘黔汞矿带脉石矿物方解石稀土元素、碳氧同位素特征及其指示意义.矿物学报,30(2):185-193.
王泽鹏,夏勇,宋谢炎,游彬,郑新华,汪小勇.2012.太平洞-紫木凼金矿区同位素和稀土元素特征及成矿物质来源探讨.矿物学报,32(1):93-100.
魏爱英.2011.滇东北毛坪铅锌矿床Ⅰ号矿群蚀变-矿化分带模式研究.昆明:昆明理工大学硕士论文,1-127.
谢卓君,夏勇,闫宝文,王泽鹏,谭亲平,伍守荣,范二川.2014.贵州省三都-丹寨成矿带中卡林型金矿地球化学特征及成矿物质来源初探.矿物岩石地球化学通报,33(3):326-333.
张鸿翔.2009.我国特色成矿系统的研究进展与重点关注的科学问题.地球科学进展,24(5):563-570.
张瑜,夏勇,王泽鹏,闫宝文,付芝康,陈明.2010.贵州簸箕田金矿单矿物稀土元素和同位素地球化学特征.地学前缘,17(2):385-395.
朱赖民,段启杉.1998.贵州西南部板其卡林型金矿床成矿过程分析.黄金,19(4):8-12.
邹明亮,王琦,李剑,梁永东,李冉.2012.多金属矿床中方解石的地球化学特征反映的成矿流体性质.地质找矿论丛,27(4):391-398.
Almqvist B S G,Herwegh M,Schmidt V,Pettke T and Hirt AM.2010.Magnetic susceptibility as a tool to study deformed calcite with variable impurity content.Geochemistry Geophysics Geosystems,11:1-15.
Alt J C.1988.The chemistry and sulfur isotope composition of massive sulfide and associated deposits on Green Seamount,eastern Pacific.Economic Geology,83(5):1026-1033.
Bau M.1991.Rare-earth element mobility during hydrothermal and metamorphic fluid-rock interaction and the significance of the oxidation state of europium.Chemical Geology,93(3-4):219-230.
Bau M,Koschinsky A,Dulski P and Hein J R.1996.Comparison of the partitioning behaviours of yttrium,rare earth elements,and titanium between hydrogenetic marine ferromanganese crusts and seawater.Geochimica et Cosmochimica Acta,60(10):1709-1725.
Bau M and M?ller P.1992.Rare earth element fractionation in metamorphogenic hydrothermal calcite,magnesite and siderite.Mineralogy and Petrology,45(3-4):231-246.
Brugger J and Meisser N.2006.Manganese-rich assemblages in the Barrhorn Unit,Turtmanntal,Central Alps,Switzerland.The Canadian Mineralogist,44(1):229-248.
Chesley J T,Halliday A N and Scrivener R C.1991.Samariumneodymium direct dating of fluorite mineralization.Science,252(2008):949-951.
Freund D,Rybacki E and Dresen G.2001.Effect of impurities on grain growth in synthetic calcite aggregates,Physics and Chemistry of Minerals,28:737-745.
Freund D,Wang Z,Rybacki E and Dresen G.2004.Hightemperature creep of synthetic calcite aggregates:Influence of Mn content.Earth and Planetary Science Letters,226:433-448.
Graf J L.1984.Effects of Mississippi Valley-type mineralization on REE patterns of carbonate rocks and minerals,viburnum trend,Southeast Missouri.Journal of Geology,92(3):307-324.
Hu R Z,Su W C,Bi X W,Tu G C and Hofstra A H.2002.Geology and geochemistry of Carlin-type Au deposits in China.Mineralium Deposita,37:378-392.
Johannesson K H,Lyons W B,Yelken M A,Gaudette H Eand Stetzenbach K J.1996.Geochemistry of rare earth elements in hypersaline and dilute acidic natural terrestrial waters:Complexation behaviour and middle rare earth element enrichment.Chemical Geology,133(1-4):124-144.
Kato Y,Fujinaga K,Nozaki T,Osawa H,Nakamura K and Ono R.2005.Rare earth,major and trace elements in the Kunimiyama ferromanganese deposit in the northern Chichibu belt,Central Shikoku,Japan.Resource Geology,55(4):291-299.
Morgan J W and Wandless G A.1980.Rare earth element in some hydrothermal minerals:Evidence for crystallographic control.Geochimica et Cosmochimica Acta,44(7):973-980.
Palmer M R.1985.Rare earth elements in foraminifera tests.Earth and Planetary Science Letters,73(2-4):285-298.
Palmer M R and Elderfield H.1986.Rare earth elements and neodymium isotopes in ferromanganese oxide coatings of Cenozoic foraminifera from the Atlantic Ocean.Geochimica et Cosmochimica Acta,50(3):409-417.
Peng J T,Hu R Z and Burnard P G.2003.Samariumneodymium isotope systematics of hydrothermal calcites from the Xikuangshan antimony deposit(Hunan,China):The potential of calcite as a geochronometer.Chemical Geology,200(1):129-136.
Sch?nenberger J,K?hler J and Markl G.2008.REE systematics of fluorides,calcite and siderite in peralkaline plutonic rocks from the Gardar Province,South Greenland.Chemical Geology,247(1-2):16-35.
Shuang Y,Bi X W,Hu R Z,Peng J T,Li H,Li D H and Zhu C S.2010.REE,Mn,Fe,Mg and C,O isotopic geochemistry of calcites from Furong tin deposit,South China:Evidence for the genesis of the hydrothermal ore-forming fluids.Resource Geology,60(1):18-34.
Su W C,Hu R Z,Xia B,Xia Y and Liu Y P.2009.Calcite Sm-Nd isochron age of the Shuiyindong Carlin-type gold deposit,Guizhou,China.Chemical Geology,258(3-4):269-274.
Su W C,Xia B,Zhang H T,Zhang X C and Hu R Z.2008.Visible gold in arsenian pyrite at the Shuiyindong Carlin-type gold deposit,Guizhou,China:Implications for the environment and processes of ore formation.Ore Geology Reviews,33(3):667-679.
Su W C,Zhang H T,Hu R Z,Ge X,Xia B,Chen Y Y and Zhu C.2012.Mineralogy and geochemistry of gold-bearing arsenian pyrite from the Shuiyindong Carlin-type gold deposit,Guizhou,China:Implications for gold depositional processes.Mineralium Deposita,47(6):653-662.
Subías I and Fernández-Nieto C.1995.Hydrothermal events in the Valle de Tena(Spanish Western Pyrenees)as evidenced by fluid inclusions and trace-element distribution from fluorite deposits.Chemical Geology,124(3-4):267-282.
Sun S S and Mc Donough W F.1989.Chemical and isotopic systematic of oceanic basalts:Implication for the mantle composition and process.Geological Society of London Special Publication,42(1):313-345.
Uysal T,Zhao J X,Golding S D,Lawrence M G,Glikson Mand Collerson K D.2007.Sm-Nd dating and rare earth element tracing of calcite:Implications for fluid-flow events in the Bowen Basin,Australia.Chemical Geology,238(1-2):63-71.
Wang J S,Wen H J,Fan H F and Zhu J J.2012.Sm-Nd geochronology,REE geochemistry and C and O isotope characteristics of calcites and stibnites from the Banian antimony deposit,Guizhou Province,China.Geochemical Journal,46(5):393-407.
Wildeman T R.1970.The distribution of Mn2+in some carbonates by electron paramagnetic resonance.Chemical Geology,5:167-177.
Yan B W,Xia Y,Wang Z P,Tan Q P,Wu S R and Fan E C.2012.Geochemical characteristics and metallogenesis of Carlin-type gold deposits in the Sandu-Danzhai metallogenic zone,Guizhou Province,China.Chinese Journal of Geochemistry,31(3):209-220.