流体包裹体的研究方法及获取的信息

SR XRF spectrum of a natural brine inclusions (pegmatite). Dotted line: blank = quartz spectrum.
Estimated concentration in ppm: Mn: 1031; Fe: 5710; Cu: 105; Zn: 1613; As: 42; Br: 76; Rb: 421; Sn: 28; Sb: 155; Cs: 886
2) electron from external electronic orbital fills the deep electronic vacancy
3) this process gives rise to X-Ray emission
X-ray
X-ray
1 to 40 kev
1
2
solid state
Vanko et al., 2001
2、单个包裹体成分分析及方法
* 激光剥蚀（消融）电感耦合等离子质 谱（LA-ICP-MS）分析
Analysis of the ionic content of fluid inclusion Laser Ablation – Inductively Coupled Plasma –Mass Spectrometry (LA-ICP-MS)
e xcit e d mat t e r vaporise d mat t e r
e je ct e d mat t e r re move d mat t e r af f e ct e d mat t e r
Analysis of the ionic content of fluid inclusions Laser Induced Breakdown Spectroscopy: LIBS
PIXE: Particles Induced X-Ray Emission
Particles = O, ....of a few MeV
particles accelerator
1) ionization of deep electronic orbital (K, L or M => Z > 11)
laser
Beamtreatment f ocusing
plasma
Collecting optics
computer
Spectrometer
Monochr omat or Polychr omat or Eche lle S pe ct r ome t e r (2 D)
PM 1D line ar I CCD
Crater obtained on quartz
Short laser pulse duration and high speed ejection of the plasma
no significant thermal diffusion in the target
Lateral resolution for macro-LIBS: 200 to 300 m
Accceleration of electron => X Ray emission 8 to 30 keV; focus of X-ray => matter interaction
1) ionization of deep electronic orbital (K, L or M => Z > 11)
Heinrich et al., 2003
Analysis of the ionic content of fluid inclusion LA-ICP-MS: limits of detection
Heinrich et al., 2003
40 m inclusion, 25 elements; > 10 g/g
1 g/g 100 ng/g 10 ng/g
8 m inclusion, 25 elements > 1wt % 1000 g/g 100 g/g
1 g/g
Analysis of the ionic content of fluid inclusion
Laser Ablation – Inductively Coupled Plasma –Mass
Limit of detection : 10 ppm for a 10 x 10 x 10 m inclusion
Analysis of the ionic content of fluid inclusion
Synchrotron X-ray Fluorescence
(Rickers et al., 2004)
Analysis of the ionic content of fluid inclusions Laser Induced Breakdown Spectroscopy: LIBS
LIBS spectrometer @ G2R
Analysis of the ionic content of fluid inclusions Laser Induced Breakdown Spectroscopy: LIBS
1、群体成分分析及方法
* 分析流程： ① 气相成分：四极质谱、气相色谱； ② 稀土及其它金属元素：ICP—MS； ③ 阴阳离子：离子色谱、原子吸收光谱、
中子活化等；
2、单个包裹体成分分析及方法
• 激光拉曼光谱法： H2O、CO2、CH4、CO、H2S、H2、N2、SO2、2H6、 C2H4、C3H8、C6H6、…… HCO3-、CO32-、SO42-、HS-…… 子矿物……
2) electron from external electronic orbital fills the deep electronic vacancy
3) this process gives rise to X-Ray emission
1
2
3
Analysis of the ionic content of fluid inclusion
PIXE
quartz background
as for SRXRF: problem of X-Ray absorption and its quantification L.OD.: Cl = Mo = Sr = 3000 ppm; Br = 50 ppm; Mn = 25 ppm; errors: 10 to 40 %
Spectrometry (LA-ICP-MS)
Heinrich et al., 2003
6 to 8 orders of magnitude in concentration depending on the detector: (TOF, quadrupole, MC)
12 natural inclusions of the same assemblage: 10-15 % RSD on the ratios
for micro-LIBS :
8 m down to 3 m
Crater obtained on copper
Depth profile dependent of the material: from 0.1 m to 6-8 m per laser shot
Analysis of the ionic content of fluid inclusions Laser Induced Breakdown Spectroscopy: LIBS
第二章 流体包裹体研究方法 及获取的信息
一、流体包裹体研究提供的信息 二、包裹体研究的准备工作 三、流体包裹体岩相学研究 四、流体包裹体测温学 五、流体包裹体成分分析 六、流体包裹体同位素分析及包裹体年代学 七、数据处理与解释
流体包裹体成分分析
1、群体成分分析及方法 2、单个包裹体成分分析及方法
1、群体成分分析及方法
2、单个包裹体成分分析及方法
* LIBS * 扫描电镜 * 电子探针
Analysis of the ionic content of fluid inclusions Laser Induced Breakdown Spectroscopy: LIBS
Laser ablation optical emission spectroscopy
EDS (Si-Li)
3
detector
spatial resolution: 1.5 m (axial) X 7 m (lateral)
Analysis of the ionic content of fluid inclusion
Synchrotron X-ray Fluorescence
(Rickers et al., 2004)
• 分析项目： • 气相成分：H2O、CO2、CH4、CO、H2S、H2、N2、……
液相成分：Na+、K+、Ca2+、Mg2+、……；CL-、HCO3-、 CO32-、SO42-……
• 微量元素：稀土及其它重金属元素； • 样品处理及加工：选矿—清洗—包体打开
[机械破碎法（压力机）、研磨法、热爆法]；
Heinrich et al., 2003
Analysis of the ionic content of fluid inclusion Laser Ablation – Inductively Coupled Plasma –Mass Spectrometry (LA-ICP-MS)
E = 2-35 J cm-2/pulse crater diameter: 2-400 m
2、单个包裹体成分分析及方法
• 傅里叶变换红外光谱法分析： （H2O、CO2、-CH2-CH3-等官能团）
2、单个包裹体成分分析及方法
* 同步辐射、X射线荧光（SXRF）分析： 分析元素从Na到REE（周期表）
Analysis of the ionic content of fluid inclusion Synchrotron X-ray Fluorescence
Analysis of the ionic content of fluid inclusions Raman spectroscopy: polyatomic ions
SO4 2- and HSO4-
Labram : Jobin-Yvon (Dilor)
Dubessy et al., 1995; Boiron et al., 1999
Detection limits estimated on liquid samples (Rusak, 1998)
H
He
Li Be
B C N O F Ne
Na Mg
Heinrich et al., 2003
பைடு நூலகம்
Analysis of the ionic content of fluid inclusion Laser Ablation – Inductively Coupled Plasma –Mass Spectrometry (LA-ICP-MS)
detector: time of flight spectrometer => quasi simultaneous detection of 68 isotopes
SR XRF spectrum of a natural brine inclusions (pegmatite). Dotted line: blank = quartz spectrum.
Estimated concentration in ppm: Mn: 1031; Fe: 5710; Cu: 105; Zn: 1613; As: 42; Br: 76; Rb: 421; Sn: 28; Sb: 155; Cs: 886
Limit of detection : 10 ppm for a 10 x 10 x 10 m inclusion
2、单个包裹体成分分析及方法
* 质子诱发X（γ）射线（PIXE和PIGE）分析： 分析测量包裹体中重元素（Z>13；氯—钠）
含量，检测限40×10-6
Analysis of the ionic content of fluid inclusion PIXE and PIGE