How to calculate mineral formula for 2 members dioctahedral mixed layers from EDX-analysis by TEM: Example - Friedland clay Nguyen, Thanh Lan*, Joern Kasbohm**, Hoang, Thi Minh Thao*** * Institute of Geography and Geology, University of Greifswald. D-17487 Greifswald, Germany; ** GeoENcon Ltd., D-17489 Greifswald, Germany *** Faculty of Geology, Hanoi University of Science, Thanh Xuan, Hanoi, Vietnam Introduction TEM ‐ Results ratio „IS : diVS“ IS‐ml diVS‐ml For more information to INTRODUCTION (purpose, sample) see below for FLYER TEM – Methodology 0.8 0.6 0.4 0.8 20 0.6 10 0.4 diVS‐ml 0 0.2 IS-ml after ~ 10,000 y (± closed system) IS‐ml 10 30 1 ratio „IS : diVS“ 0 = randomly interstratified illite-smectite mixed layer phase (see INTRODUCTION) 0.2 Interlayer charge for certain members of IS-ml Interlayer charge for certain members of diVS-ml diVS-ml = dioctahedral vermiculite-smectite mixed layer phase (see INTRODUCTION) Interlayer ccharge (O10(OH)2 ) 40 diVS‐ml IS‐ml diVS‐ml 20 (e.g. small different in ratio ‚IS-ml vs. diVS-ml‘ as indicator for that) IS‐ml diVS‐ml 30 BUT # parameter ‚open system‘ (rain water) could exceed parameter ‚time‘ in comparison to ‚closed systems‘ (glacial water) after few decades of years already impact by glacial water 1 after < 10 y (± open system) Fre equency (%) 40 (check ratio and missing smectite-rich members of diVS-ml in diagram ‚impact by glacial water‘) 0.2 IS‐ml HOW IS THIS PROCESS TO RECOGNIZE? Here: TEM – particle‐wise EDX‐analyses – see TEM‐Methodology and TEM‐Results XRD – oriented mounts (EG) – see XRD‐Proofs Fre equency (%) diVS‐ml = K‐deficient IS‐ml diVS‐ml = charge‐deficient IS‐ml commonly VIAl3+‐enriched ratio „IS : diVS“ 4. Rate of Alteration # deepest degree by glacial water impact representing parameter ‚time‘ Illite 0 impact by rain water IS‐ml in senso of Środon et al. 1992 interlayer charge of illite: 0.89 interlayer charge of smectite: 0.40 diVS‐ml 0.4 ML80 Mg 3. Illitization # diVS-ml show a higher degree of illitization (compare the different maxima for IS-ml and diVS-ml) ML60 2+ 0.6 10 ML40 + 0.8 IS‐ml Mg22+ diVS-ml) ML20 Fe 4+ reduced Si Si 4+ reduced 20 Montm. Mg2+ 3+ 2. Interlayer Charge # diVS-ml show a reduced interlayer charge (check for IS-ml vs. for Interlayer ccharge (O10(OH)2) IS-ml + Al 3+ diVS S-ml increased Al increased Al3+3+ Frequency (%) (see small ratio-bars in left corners of each diagram) What is to recognize here? 1 origin Interlay yer charge ((O10(OH)2) 30 1. Ratio ‚IS-ml : diVS-ml‘ # IS-ml is altering into diVS-ml ML80 ML20 What is to recognize here? diVerm Changing of ratio IS‐ml and diVS‐ml and interlayer charge ML60 Alteration of illite‐smectite mixed layer phases (IS‐ml) into dioctahedral vermiculite‐smectite mixed layer phases (diVS‐ml) ML40 FREQUENCY / DIVERSITY OF IS‐ml AND diVS‐ml Montm. INTERACTION OF CLAY AND WATER . ML10 = 10% of illitic layers in this class of ml XRD – Proofs ŚRODON et al., 1992: S , ( ) max (%) DETERMINES CHEMISTRY ALTERATION OF SWELLING PHASE VIA RATIO ‘17Å:10Å’ concerning IVAl3+, XIIK (FIX) and interlayer charge in XRD patterns from ethylene glycol saturated (EG) specimen origin 2.86 EG d=17Å, Illite e < d=17Å, IS-ml Ratio ‚17Å:10Å‘ # Height of 17Å-peaks is decreasing in comparison to mica (10Å) d=7Å, Kaolinite < What is to recognize here? rain water impact after < 10 y (± open system) after ~ 10,000 y (± closed system) from 600 Å to 120 Å per stack from 400 Å to 90 Å per stack Illite from 60 Å to 45 Å per stack + Illite – Smectite and dioctahedral Vermiculite – Smectite mixed layer phases show mostly a lognormal distribution + Illite – Smectite mixed layer altered into dioctahedral Vermiculite – Smectite mixed layer phases in contact with water + duration d ti off contact t t is i determining d t i i the th degree d off alteration: lt ti glacial l i l water t (~ 10,000 10 000 y)) > rain i water t (< ( 10 y)) + alteration could be faster in open systems than in closed system (see high degree of alteration already after < 10 years in contact with rain water) + selective exploitation is now possible , e.g. to offer optimized products for UV‐protection creams and for filtering of vegetable oil (low charges required) = particle‐wise TEM‐EDX analysis is a very sensitive tool to recognize alteration processes in clay mineral matter Acknowledgments We thank colleagues of TEM‐laboratory at Institute of Geography and Geology (Greifswald). Funding for this project was provided by GRS mbH. d=10Å, Illite d=7Å, Kaolinite XRD by y J. Kroos IS-ml diVS-ml 1.31 < d=17Å, IS-ml d=7Å, Kaolinite d=10Å, Illite d=17Å, IS-ml < Characterization of Peak Shape (by Dehlez et al. (1993) Conclusions Contact email: [email protected] glacial water impact < < What is the proof for reduction of thickness? Already 1 month contact time with water is reducing the thickness of EG-saturated (001) BRAGG peak: For more information to TEM-METHODOLOGY (equations, control-values) see below for FLYER Reduced thickness of particles # Interpretation: Reduction of particle thickness during alteration of IS-ml into diVS-ml by breaking at smectitic interlayers and lower interlayer charge than in IS-ml EG EG 2.00 What is the interpretation?
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