The Dulong deposit,located in the Laojunshan area of southeastern Yunnan,China,is an important polymetallic deposit due to its high reserves of tin,zinc,and indium.The occurrence state of indium is critical for unders...The Dulong deposit,located in the Laojunshan area of southeastern Yunnan,China,is an important polymetallic deposit due to its high reserves of tin,zinc,and indium.The occurrence state of indium is critical for understanding its supernormal enrichment mechanism.Previous studies investigated the occurrence state of indium(including the valence state)based on the indium content in sphalerite and the correlation between metal concentrations.However,more evidence is needed to better constrain indium occurrence at the micro-,nano-,or even atomic scale.In this study,EPMA-FIB-SEM-TEM and XPS techniques were employed to investigate the indium distribution characteristics and occurrence state in sphalerite from the Dulong Sn–Zn–In polymetallic deposit.The maximum concentration of indium in the indium-rich sphalerite samples is 0.37%,and the results of the EPMA analysis showed a relatively homogeneous distribution of indium in sphalerite.The FIB-SEM-TEM results demonstrated that the lattice stripes of sphalerite were periodically and continuously distributed at the nanoscale,confirming that sphalerite in the deposit was an excellent single crystal structure,and the peak heights of the various characteristic peaks of indium in the EDX spectra were relatively close to each other,with no distinct peaks of high indium content.In addition,the XPS results indicate that the element valence state of indium in sphalerite is In^(3+),and it combines with S^(2-)to form a bond.These results indicate that indium in sphalerite of the Dulong deposit is uniformly distributed at both the micro-and nanoscale,and there is no indium-independent mineral.In^(3+)enters the crystal lattice of sphalerite by replacing Zn2+in the form of isomorphic substitution.展开更多
都龙锡锌铟多金属矿床位于著名的滇东南钨锡多金属成矿区之老君山矿集区,成矿与白垩纪大规模花岗岩活动关系密切,沿隐伏花岗岩接触带周边发育石榴子石、透辉-透闪石等矽卡岩蚀变和条带状(似层状)、脉状(囊状)的锡石、闪锌矿及磁铁矿、...都龙锡锌铟多金属矿床位于著名的滇东南钨锡多金属成矿区之老君山矿集区,成矿与白垩纪大规模花岗岩活动关系密切,沿隐伏花岗岩接触带周边发育石榴子石、透辉-透闪石等矽卡岩蚀变和条带状(似层状)、脉状(囊状)的锡石、闪锌矿及磁铁矿、辉钼矿、黄铁黄铜矿等矿化,形成超大规模的岩浆热液-矽卡岩成矿系统。野外观测及研究发现,早期(矽卡岩期)高温阶段形成的磁铁矿可分为I阶段交代型磁铁矿(I-Mag)和II阶段充填型磁铁矿(II-Mag)两类:前者多呈囊状、条带状,与矽卡岩矿物共生;后者为脉状,与金属硫化矿物共生。利用ICP-AES、ICP-MS对两类磁铁矿进行主、微量元素测试,从I-Mag到II-Mag,Si、Ca、Mn及ΣREE、Pb、Zn、Ti含量增加,Mg及Sn、W、In、V、Cr、Ga含量减少,REE配分型式也由平缓向右倾的逐渐变化。TiO 2-Al 2 O 3-(MgO+MnO)、(Ti+V)-(Ca+Al+Mn)、Ni/Cr-Ti、(Ti+V)-Ni/(Cr+Mn)成因判别图解表明,磁铁矿属岩浆热液-矽卡岩成因类型;Ti、V与Zr、Hf、Nb、Ta,以及Y/Ho(24~3414)、Ni/Co(<2→>2)、Ti/V(<25→>25)、Hf/Zr(003~006→004~005)存在着线性关系和规律变化特征,指示两类型磁铁矿具有相同的物质来源,为同一成矿过程不同阶段的产物。而代表成矿流体REE组成的II-Mag的REE组成继承了老君山花岗岩REE配分趋势和Eu负异常特征,表明磁铁矿与白垩纪老君山花岗岩具有一致的物质来源。Cr-V、(Ti+V)-(Al+Mn)、Ga-Mg及Ga-Sn图解显示相同的成因类型和一致的线性关系,指示磁铁矿主体形成于较高氧逸度和温度(约300℃)的成矿环境下,并且从I-Mag到II-Mag,存在着氧逸度逐渐升高、温度逐渐降低的演化趋势。展开更多
基金financially supported by the National Nature Science Foundation of China(42072094,42162012)。
文摘The Dulong deposit,located in the Laojunshan area of southeastern Yunnan,China,is an important polymetallic deposit due to its high reserves of tin,zinc,and indium.The occurrence state of indium is critical for understanding its supernormal enrichment mechanism.Previous studies investigated the occurrence state of indium(including the valence state)based on the indium content in sphalerite and the correlation between metal concentrations.However,more evidence is needed to better constrain indium occurrence at the micro-,nano-,or even atomic scale.In this study,EPMA-FIB-SEM-TEM and XPS techniques were employed to investigate the indium distribution characteristics and occurrence state in sphalerite from the Dulong Sn–Zn–In polymetallic deposit.The maximum concentration of indium in the indium-rich sphalerite samples is 0.37%,and the results of the EPMA analysis showed a relatively homogeneous distribution of indium in sphalerite.The FIB-SEM-TEM results demonstrated that the lattice stripes of sphalerite were periodically and continuously distributed at the nanoscale,confirming that sphalerite in the deposit was an excellent single crystal structure,and the peak heights of the various characteristic peaks of indium in the EDX spectra were relatively close to each other,with no distinct peaks of high indium content.In addition,the XPS results indicate that the element valence state of indium in sphalerite is In^(3+),and it combines with S^(2-)to form a bond.These results indicate that indium in sphalerite of the Dulong deposit is uniformly distributed at both the micro-and nanoscale,and there is no indium-independent mineral.In^(3+)enters the crystal lattice of sphalerite by replacing Zn2+in the form of isomorphic substitution.
文摘都龙锡锌铟多金属矿床位于著名的滇东南钨锡多金属成矿区之老君山矿集区,成矿与白垩纪大规模花岗岩活动关系密切,沿隐伏花岗岩接触带周边发育石榴子石、透辉-透闪石等矽卡岩蚀变和条带状(似层状)、脉状(囊状)的锡石、闪锌矿及磁铁矿、辉钼矿、黄铁黄铜矿等矿化,形成超大规模的岩浆热液-矽卡岩成矿系统。野外观测及研究发现,早期(矽卡岩期)高温阶段形成的磁铁矿可分为I阶段交代型磁铁矿(I-Mag)和II阶段充填型磁铁矿(II-Mag)两类:前者多呈囊状、条带状,与矽卡岩矿物共生;后者为脉状,与金属硫化矿物共生。利用ICP-AES、ICP-MS对两类磁铁矿进行主、微量元素测试,从I-Mag到II-Mag,Si、Ca、Mn及ΣREE、Pb、Zn、Ti含量增加,Mg及Sn、W、In、V、Cr、Ga含量减少,REE配分型式也由平缓向右倾的逐渐变化。TiO 2-Al 2 O 3-(MgO+MnO)、(Ti+V)-(Ca+Al+Mn)、Ni/Cr-Ti、(Ti+V)-Ni/(Cr+Mn)成因判别图解表明,磁铁矿属岩浆热液-矽卡岩成因类型;Ti、V与Zr、Hf、Nb、Ta,以及Y/Ho(24~3414)、Ni/Co(<2→>2)、Ti/V(<25→>25)、Hf/Zr(003~006→004~005)存在着线性关系和规律变化特征,指示两类型磁铁矿具有相同的物质来源,为同一成矿过程不同阶段的产物。而代表成矿流体REE组成的II-Mag的REE组成继承了老君山花岗岩REE配分趋势和Eu负异常特征,表明磁铁矿与白垩纪老君山花岗岩具有一致的物质来源。Cr-V、(Ti+V)-(Al+Mn)、Ga-Mg及Ga-Sn图解显示相同的成因类型和一致的线性关系,指示磁铁矿主体形成于较高氧逸度和温度(约300℃)的成矿环境下,并且从I-Mag到II-Mag,存在着氧逸度逐渐升高、温度逐渐降低的演化趋势。
