石榴子石Fe~(3+)含量电子探针原位分析:Flank Method方法的实例应用
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摘要
电子探针分析技术主要应用于对物质进行快速无损的定性、定量分析,是材料科学和地质学领域最基础和重要的研究手段。而利用电子探针对矿物中不同价态Fe的含量进行原位定量分析,更是具有非常重要的科学意义。近来发展起来的可进行Fe~(3+) 含量定量分析的电子探针Flank Method测试方法,相比早期的实验方法具有更高的准确度和精确性。该方法主要是通过定义Fe的特征X射线L能级谱线峰位的峰侧位置(flank position),对应了不同价态Fe吸收谱线的差值线谱(difference spectrum)中强度计数最大值(FeLα*)和最小值(FeLβ*)的位置,从而避免了在早期实验中,一般通过直接测量Fe的L能级峰位(FeLα和FeLβ)可能导致的测试不确定性。同时,该测试方法通过对电子探针谱仪系统进行实时的位移误差校正,确保其在某一个稳定的实验条件(周期)下具有可重现性(精确度)。在本文中,我们根据北京大学造山带与地壳演化教育部重点实验室的JEOL JXA-8100型号电子探针的实际性能状态,在前人建立的实验步骤基础上,进行了测试流程的自适性改进和修正,建立了更符合本实验室实际情况的电子探针Flank Method测试方法,用于分析石榴子石中的Fe~(3+) 含量。通过对已知Fe~(3+) 含量的标准石榴子石样品进行检测验证,确定了该方法的可行性、可靠性以及可重复性。在对天然样品的分析中,我们选择了来自我国天山、拉萨和北祁连的洋壳俯冲类型中低温(超)高压榴辉岩中的石榴子石样品,对其进行了Fe~(3+) 含量(环带)的分析。结果显示,石榴子石中Fe~(3+) 含量可作为一个可靠的氧逸度指示剂,其(环带)变化很好地对应了榴辉岩寄主岩石的变质演化轨迹,反映了在板片俯冲过程中,榴辉岩的氧逸度具有降低的趋势。
The electron microprobe( EMP) analysis is a quick and non-destructive method for qualitative and quantitative analyses upon samples from material science and geoscience,which plays a fundamental and vital role in these subjects. It is of great scientific significance in the geological research to use EMP to determine the in-situ contents of Fe with different valences( ferric and ferrous) in minerals. The newly developed microprobe-based Flank Method measurement to quantify the Fe~(3+) content in minerals is comparatively of much higher precision and greater credibility than the early experimental approaches. The Flank Method measures the defined flank positions instead of the actual peaks of the iron's X-ray characteristic L emission spectra( FeL); those flank positions correspond to the maxima( Fe α*) and minima( FeLβ*) values of the iron's absorption difference spectrum. Meanwhile,a spectrometer calibration procedure is designed for the peak shift error correction prior to the Flank Method measurement in order to maintain the analytical reliability and reproducibility. This calibration procedure should be performed in each working session within a proper time duration. In this work,we propose a modified and improved Flank Method measuring procedure after the early suggestions,to analyze the Fe~(3+) content in the garnet by using JEOL JXA-8100 microprobe in our facility. The feasibility,reliability and repeatability of this method has been well tested on several standard garnets with known Fe~(3+) contents in our laboratory,and then it is applied on some natural garnet samples. The analyzed garnets are from the typical oceanic subduction type medium-low temperature and( ultra-) highpressure eclogites of SW Tianshan( Habutengsu),Lhasa terrane( Songduo area) and North Qilian( Baijingsi foliate zone). The results show that the Fe~(3+) content serves a good indicator of the oxidation state,and its( zonal) change in garnet corresponds to the metamorphic P-T path,suggesting that the oxygen-fugacity is probably prone to decline in the subduction process.
The electron microprobe( EMP) analysis is a quick and non-destructive method for qualitative and quantitative analyses upon samples from material science and geoscience,which plays a fundamental and vital role in these subjects. It is of great scientific significance in the geological research to use EMP to determine the in-situ contents of Fe with different valences( ferric and ferrous) in minerals. The newly developed microprobe-based Flank Method measurement to quantify the Fe~(3+) content in minerals is comparatively of much higher precision and greater credibility than the early experimental approaches. The Flank Method measures the defined flank positions instead of the actual peaks of the iron's X-ray characteristic L emission spectra( FeL); those flank positions correspond to the maxima( Fe α*) and minima( FeLβ*) values of the iron's absorption difference spectrum. Meanwhile,a spectrometer calibration procedure is designed for the peak shift error correction prior to the Flank Method measurement in order to maintain the analytical reliability and reproducibility. This calibration procedure should be performed in each working session within a proper time duration. In this work,we propose a modified and improved Flank Method measuring procedure after the early suggestions,to analyze the Fe~(3+) content in the garnet by using JEOL JXA-8100 microprobe in our facility. The feasibility,reliability and repeatability of this method has been well tested on several standard garnets with known Fe~(3+) contents in our laboratory,and then it is applied on some natural garnet samples. The analyzed garnets are from the typical oceanic subduction type medium-low temperature and( ultra-) highpressure eclogites of SW Tianshan( Habutengsu),Lhasa terrane( Songduo area) and North Qilian( Baijingsi foliate zone). The results show that the Fe~(3+) content serves a good indicator of the oxidation state,and its( zonal) change in garnet corresponds to the metamorphic P-T path,suggesting that the oxygen-fugacity is probably prone to decline in the subduction process.
引文
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H?fer HE and Brey GP.2007.The iron oxidation state of garnet by electron microprobe:Its determination with the flank method combined with major-element analysis.American Mineralogist,92(5-6):873-885
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Li XL,Song SG,Zhang LF and H?fer EH.2018.Application of microprobe-based flank method analysis of Fe3+in garnet of North Qilian eclogite and its geological implication.Science Bulletin,63(5):300-305
Liu Y,Santosh M,Yuan TY,Li HQ and Li TF.2016.Reduction of buried oxidized oceanic crust during subduction.Gondwana Research,32:11-23
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LüZ,Zhang LF,Du JX and Bucher K.2009.Petrology of coesitebearing eclogite from Habutengsu Valley,western Tianshan,NWChina and its tectonometamorphic implication.Journal of Metamorphic Geology,27(9):773-787
LüZ,Zhang LF,Du JX,Yang X,Tian ZL and Xia B.2012a.Petrology of HP metamorphic veins in coesite-bearing eclogite from western Tianshan,China:Fluid processes and elemental mobility during exhumation in a cold subduction zone.Lithos,136-139:168-186
LüZ,Bucher K,Zhang LF and Du J.2012b.The Habutengsu metapelites and metagreywackes in western Tianshan,China:Metamorphic evolution and tectonic implications.Journal of Metamorphic Geology,30(9):907-926
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Cao Y,Song SG,Niu YL,Jung H and Jin ZM.2011.Variation of mineral composition,fabric and oxygen fugacity from massive to foliated eclogites during exhumation of subducted ocean crust in the North Qilian suture zone,NW China.Journal of Metamorphic Geology,29(7):699-720
Creighton SD,Matveev S,Stachel T and Luth RW.2004.Electron microprobe analysis of Fe2+/Fe3+in minerals with low total iron concentrations.In:American Geophysical Union,Fall Meeting2004.Washington:AGU
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Dyar MD,Guidorttri CV,Holdaway MJ and CoLucci M.1993.Nonstoichiometric hydrogen contents in common rock-forming hydroxyl silicates.Geochimica et Cosmochimica Acta,57(12):2913-2918
Dyar MD,Agresti DG,Schaefer MW,Grant CA and Sklute EC.2006.M9ssbauer spectroscopy of Earth and planetary materials.Annual Review of Earth and Planetary Sciences,34:83-125
Dyar MD,Breves EA,Emerson E,Bell SW,Nelms M,Ozanne MV,Peel SE,Carmosino ML,Tucker JM,Gunter ME,Delaney JS,Lanzirotti A and Woodland AB.2012.Accurate determination of ferric iron in garnets by bulk M9ssbauer spectroscopy and synchrotron micro-XANES.American Mineralogist,97(10):1726-1740
Fischer DW and Baun WL.1968.Band structure and the Titanium LII,IIIX-ray emission and absorption spectra from pure metal,oxides,nitride,carbide,and boride.Journal of Applied Physics,39(10):4757-4776
H?fer HE,Brey GP,Schulz-Dobrick B and Oberhnsli R.1994.The determination of the oxidation state of iron by the electron microprobe.European Journal of Mineralogy,6(3):407-418
H?fer HE,Weinbruch S,Mc Cammon CA and Brey GP.2000.Comparison of two electron probe microanalysis techniques to determine ferric iron in synthetic wüstite samples.European Journal of Mineralogy,12(1):63-71
H?fer HE.2002.Quantification of Fe2+/Fe3+by electron microprobe analysis:New developments.Hyperfine Interactions,144-145(1-4):239-248
H?fer HE and Brey GP.2007.The iron oxidation state of garnet by electron microprobe:Its determination with the flank method combined with major-element analysis.American Mineralogist,92(5-6):873-885
Johnson WM and Maxwell JA.1981.Rock and Mineral Analysis.New York:Wiley
Lalonde AE,Rancourt DG and Ping JY.1998.Accuracy of ferric/ferrous determinations in micas:A comparison of M9ssbauer spectroscopy and the Pratt and Wilson wet-chemical methods.Hyperfine Interactions,117(1-4):175-204
Li YL,Zheng YF and Fu B.2005.M9ssbauer spectroscopy of omphacite and garnet pairs from eclogites:Application to geothermobarometry.American Mineralogist,90(1):90-100
Li XL,Song SG,Zhang LF and H?fer EH.2018.Application of microprobe-based flank method analysis of Fe3+in garnet of North Qilian eclogite and its geological implication.Science Bulletin,63(5):300-305
Liu Y,Santosh M,Yuan TY,Li HQ and Li TF.2016.Reduction of buried oxidized oceanic crust during subduction.Gondwana Research,32:11-23
Locock AJ.2008.An Excel spreadsheet to recast analyses of garnet into end-member components,and a synopsis of the crystal chemistry of natural silicate garnets.Computers&Geosciences,34(12):1769-1780
Luth RW,Virgo D,Boyd FR and Wood BJ.1990.Ferric iron in mantlederived garnets:Implications for thermobarometry and for the oxidation state of the mantle.Contributions to Mineralogy and Petrology,104(1):56-72
LüZ,Zhang LF,QüJF and Li HJ.2007.Petrology and metamorphic P-T path of eclogites from Habutengsu,southwestern Tianshan,Xinjiang.Acta Petrologica Sinica,23(7):1617-1626(in Chinese with English abstract)
LüZ,Zhang LF,Du JX and Bucher K.2009.Petrology of coesitebearing eclogite from Habutengsu Valley,western Tianshan,NWChina and its tectonometamorphic implication.Journal of Metamorphic Geology,27(9):773-787
LüZ,Zhang LF,Du JX,Yang X,Tian ZL and Xia B.2012a.Petrology of HP metamorphic veins in coesite-bearing eclogite from western Tianshan,China:Fluid processes and elemental mobility during exhumation in a cold subduction zone.Lithos,136-139:168-186
LüZ,Bucher K,Zhang LF and Du J.2012b.The Habutengsu metapelites and metagreywackes in western Tianshan,China:Metamorphic evolution and tectonic implications.Journal of Metamorphic Geology,30(9):907-926
Mc Guire AV,Dyar MD and Ward KA.1989.Neglected Fe3+/Fe2+ratios:A study of Fe3+content of megacrysts from alkali basalts.Geology,17(8):687-690
Mc Guire AV,Francis CA and Dyar MD.1992.Mineral standards for electron microprobe analysis of oxygen.American Mineralogist,77:1087-1091
Pavic'evic'MK,Amthauer G and El Goresy A.1989.X-ray L-emmission spectra of iron in silicate garnets.Journal of the Serbian Chemical Society,54:359-371
Quinn RJ,Valley JW,Page FZ and Fournelle JH.2016.Accurate determination of ferric iron in garnets.American Mineralogist,101(7):1704-1707
Raeburn SP,Ilton ES and Veblen DR.1997.Quantitative determination of the oxidation state of iron in biotite using X-ray photoelectron spectroscopy:I.Calibration.Geochimica et Cosmochimica Acta,61(21):4519-4530
Rankenburg K,Lassiter JC and Brey G.2004.Origin of megacrysts in volcanic rocks of the Cameroon volcanic chain:Constraints on magma genesis and crustal contamination.Contributions to Mineralogy and Petrology,147(2):129-144
Rickwood PC.1968.On recasting analyses of garnet into end-member molecules.Contributions to Mineralogy and Petrology,18(2):175-198
Schingaro E,Lacalamita M,Mesto E,Ventruti G,Pedrazzi G,Ottolini Land Scordari F.2016.Crystal chemistry and light elements analysis of Ti-rich garnets.American Mineralogist,101(2):371-384
Schmid R,Wilke M,Oberhnsli K,Janssens K,Falkenberg G,Franz Land Gaab A.2003.Micro-XANES determination of ferric iron and its application in thermobarometry.Lithos,70(3-4):381-392
Sobolev NV,Schertl HP,Valley JW,Page FZ,Kita NT,Spicuzza MJ,Neuser RD and Logvinova AM.2011.Oxygen isotope variations of garnets and clinopyroxenes in a layered diamondiferous calcsilicate rock from Kokchetav Massif,Kazakhstan:A window into the geochemical nature of deeply subducted UHPM rocks.Contributions to Mineralogy and Petrology,162(5):1079-1092
Sobolev VN,Mc Cammon CA,Taylor LA,Snyder GY and Sobolev NV.1999.Precise M9ssbauer milliprobe determination of ferric iron in rock-forming minerals and limitations of electron microprobe analysis.American Mineralogist,84(1-2):78-85
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