微量元素的地球化学分类

1、微量元素地球化学Trace Element Geochemistry 按照Goldschmidt法则, 根据元素在共存的硅酸盐流体相、硫化物流体相、金属流体相和气相之间的分配特征，将元素进行分类。硫化物流体金属流体气相亲铁元素亲铜/硫元素亲石元素亲气元素H, He, N, Noble gasesAlkalis, Alkaline Earths, Halogens, B, O, Al, Si, Sc, Ti, V, Cr, Mn, Y, Zr, Nb, Lanthanides, Hf, Ta, Th, UCu, Zn, Ga, Ag, Cd, In, Hg, Tl, As, S, Sb, Se,

2、 Pb, Bi, TeFe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Mo, Re, Au, C, P, Ge, Sn Melting a chondrite gives 3 immiscible liquids plus vapor:硅酸盐流体Why？What makes an element siderophile or lithophile? Notably, the Goldschmidt categories are well-grouped in the periodic table of the elements:HLiNaKRbCsFrBeMgCaSrB

3、aRaScYTiZrHfRfVNbTaDbCrMoWSgMnTcReBhFeRuOsHsCoRhIrMtNiPdPtCuAgAuZnCdHgGaInTlGeSnPbAsSbBiSeTePoBrIAtKrXeRnBAlCSiNPOSFClNeArHeLaAcCeThPrPaNdUPmNpSmPuEuAmGdCmTbBkDyCfHoEsErFmTmMdYbNoLuLr1234567IAIIAIIIA IVAVAVIAVIIA VIIIAIIIB IVBVBVIBVIIBVIIIBIBIIBLanthanidesActinides13111937558741220385688213922407210

4、4234173105244274106254375107264476108274577109284678294779304880513314981614325082715335183816345284917355385101836548625789589059916092619362946395649665976698679968100691017010271103AtmophileLithophileChalcophileSiderophileArtificialFirst Ionization Potentials of the ElementsCsRbKNaLiRnXeKrArNeHeF

5、rRaPuBCOFMgAlSiClCaFeGaGeBrSnIAuHgLu0510152025Noble GasesAlkali MetalsRare EarthsPauling Electronegativity of the ElementsAtLuHgAuISnBrGeGaFeCaClSiAlMgFOCBPuAcRaHeNeArKrXeRaLiNaKRbCsFrUChalcophileSiderophileLithophileAtmophile00.511.522.533.540102030405060708090100Z ZNoble GasesAlkali MetalsRare Ear

6、thsHalogensFirst Ionization Potential (eV)Pauling ElectronegativityiiDDRT/ )(iiiiiiiiiiiiiiK)P,T(KeRTlnRTlnRTlnRTlnii标准化学势 热力学活度Thermodynamic activity 摩尔气体常数 iixi摩尔浓度 活度系数),(TPiiiiiKxx),(TPiiiiiKxx),(TPiiiKxx1*pipiiiixxandxxDMolar partition (Nernst) coefficientpiipiiiipiiiiiiipiiiipiiiiiiMcMcDDMcMcx

7、WcwMwMwnnxMwn*在给定温度、压力和除i外的其它元素含量条件下，Nernst分配系数是一个常数1*pipiiiixxandxxDpiipiiiiMcMcDD*meltolMgDNiK/微量元素地质温度微量元素地质温度计和地质压力计计和地质压力计1.1.离子电价离子电价 与被置换元素的离子半径相与被置换元素的离子半径相差大的优先进入溶液差大的优先进入溶液/ /熔体熔体2.2.离子半径；离子半径；体系总成分的影响在1400oC、1个大气压下，Nb在金红石和熔体之间的分配系数对K*的依赖性以及与Nb含量之间的关系。K* = K2O/(K2O + Al2O3)摩尔数之比Horng W.S.

8、and Hess P.S., CMP, (2000) 138: 176-185Seitz et al.(1999), GCA, 63: 39673982,橄榄岩中过渡元橄榄岩中过渡元素在素在cpxcpx和和opxopx之之间的分配系数随间的分配系数随温度的变化温度的变化K = DK = Dcpxcpx/D/Dopxopx= = C Ccpxcpx/C/CopxopxTrace element distribution coefficients between zircon and garnet. a) Own data for different temperatures. 1 sigma e

9、rrors for Gd, Y, Er, Yb and Lu are reported in grey beside the symbols. b) Own experimental data compared to literature data for different rock types. Sources: tw = this work; Rub&Her = Monviso HP vein of Rubatto and Hermann (2003); Her&Rub = Malenco granulite of Hermann and Rubatto (2003); Rub = Re

10、ynolds granulite of Rubatto (2002); Bui et al. = Limpopo granulite of Buick et al. (2006); Rub et al. = Stafford granulite of Rubatto et al. (2006); Whi&Plat = Betic granulite of Whitehouse and Platt (2003); Hok&Har = UHT rock of Hokada and Harley (2004); Kel et al. = UHT rock of Kelly and Harley (2

11、005).Rubatto and Hermann, 2007, CGZong et al., 2010, CG ！适用范围和条件！适用范围和条件Lee et al., 2007, GCAOlivineOpxCpxGarnetPlagAmph MagnetiteRb0.0100.0220.0310.0420.0710.29 Sr0.0140.0400.0600.0121.8300.46 Ba0.0100.0130.0260.0230.230.42 Ni14570.9550.016.829Cr0.7010341.3450.012.007.4La0.0070.030.0560.0010.1480.5

12、442Ce0.0060.020.0920.0070.0820.8432Nd0.0060.030.2300.0260.0551.3402Sm0.0070.050.4450.1020.0391.8041Eu0.0070.050.4740.243 0.1/1.5*1.5571Dy0.0130.150.5821.9400.0232.0241Er0.0260.230.5834.7000.0201.7401.5Yb0.0490.340.5426.1670.0231.6421.4Lu0.0450.420.5066.9500.0191.563Data from Rollinson (1993).* Eu3+/

13、Eu2+Italics are estimatedRare Earth ElementsPartition Coefficients (CS/CL) for Some Commonly Used TraceElements in Basaltic and Andesitic RocksAB12nijjiDiKDOlivineOpxCpxGarnetPlagAmph MagnetiteRb0.0100.0220.0310.0420.0710.29 Sr0.0140.0400.0600.0121.8300.46 Ba0.0100.0130.0260.0230.230.42 Ni14570.9550

14、.016.829Cr0.7010341.3450.012.007.4La0.0070.030.0560.0010.1480.5442Ce0.0060.020.0920.0070.0820.8432Nd0.0060.030.2300.0260.0551.3402Sm0.0070.050.4450.1020.0391.8041Eu0.0070.050.4740.243 0.1/1.5*1.5571Dy0.0130.150.5821.9400.0232.0241Er0.0260.230.5834.7000.0201.7401.5Yb0.0490.340.5426.1670.0231.6421.4Lu

15、0.0450.420.5066.9500.0191.563Data from Rollinson (1993).* Eu3+/Eu2+Italics are estimatedRare Earth ElementsDifjjDij/melt离子半径10-1nmNb5+0.48-0.74Ta5+0.64-0.74Zr4+0.59-0.89Hf4+0.58-0.83Ti4+0.42-0.74P4+0.17-0.38U4+0.89-1.17U5+0.76-0.84U6+0.45-0.86Th4+0.94-1.21Pb2+0.98-1.45Pb4+0.65-0.94LILEHFSE特例特例Tecton

16、ic Setting from distinctive trace element patterns Multi-Element Diagrams 对于火山岩，对于火山岩，A和和B哪一个反映分馏结晶作哪一个反映分馏结晶作用程度增加的方向，哪一个反映部分熔融作用程度增加的方向，哪一个反映部分熔融作用程度增加的方向？用程度增加的方向？AB？一块受到严重风化作用的玄武岩，其中的Cs、Sr、Zr、Hf、Nb、Ta在剖面A-B上的含量变化特征如何？AB （Gd以后以后4f电子自旋方向相反）电子自旋方向相反）91500Zong et al., 2007REEREE离子半径离子半径REE (3+)的离子半的

17、离子半径径. Pm 没没有半衰期有半衰期大于大于5年的年的同位素。同位素。Eu2+Ce4+玄武岩玄武岩体系中矿物熔体间REE的分配系数(McKenzie and ONions, 1991)。各种矿物在流纹岩/英安岩体系中的分配系数(Bacon and Druitt, 1988; Irving and Frey, 1978; Nash and Crecraft, 1985) OlivineOpxCpxGarnetPlagAmph MagnetiteRb0.0100.0220.0310.0420.0710.29 Sr0.0140.0400.0600.0121.8300.46 Ba0.0100.01

18、30.0260.0230.230.42 Ni14570.9550.016.829Cr0.7010341.3450.012.007.4La0.0070.030.0560.0010.1480.5442Ce0.0060.020.0920.0070.0820.8432Nd0.0060.030.2300.0260.0551.3402Sm0.0070.050.4450.1020.0391.8041Eu0.0070.050.4740.243 0.1/1.5*1.5571Dy0.0130.150.5821.9400.0232.0241Er0.0260.230.5834.7000.0201.7401.5Yb0.

19、0490.340.5426.1670.0231.6421.4Lu0.0450.420.5066.9500.0191.563Rare Earth Elements相容性增强相容性增强原子数增加原子数增加-3-2-1012345678910110102030405060708090100Atomic Number (Z)Log (Abundance in CI Chondritic Meteorite)HHeLiBeBCNOFScFeNiNeMgSiSCaArTiPbPtSnBaVKNaAlPClThUREE5758596062636465666768697071LaCePrNdSmEuGdTbDyHoErTmYbLu0.1110Concentration (ppm)LaCePrNdSmEuGdTbDyHoErTmYbLu0.1110Concentration (ppm)LaCePrNdSmEuGdTbDyHoErTmYbLu0.1110Chondrite-Normalized ValueLaCePrNdSmEuGdTbDyHoErTmYbLu0.1110Concentration (ppm)LaCePrNdSmEuGdTbDyHoErTmYbLu1