Szöőr, Gyula

English

Combination of a home-made thermoanalytical device (Derivatograph, MOM) and a quadrupole mass spectrometer (QMS-D, ATOMKI) is presented, and the simultaneous thermoanalytical method (DTA, DTG, TG, QMS-EGA) has been successfully applied in many fields of mineralogy, petrology, geochemistry and chemostratigraphy. In Hungary, positive experience has been obtained in the following fields: — determination of rare mineral in the Carpathian Basin. — Diagenetic and hydrothermal processes and facies were characterized by distinguished mineral associations in Hungary and Cuba. — Geological dating by investigations of sporadic finds (bones) of Neogene vertebrates

Szöőr Gyula

University of Szeged

Acta Mineralogica-Petrographica, Szeged, XXXI, 57—65, ¡990 A N A P P A R A T U S F O R S I M U L T A N E O U S T H E R M A L A N A L Y S I S A N D I T S A P P L I C A T I O N I N G E O L O G I C A L R E S E A R C H G . S Z Ö Ö R * L. Kossuth University, Department of Mineralogy and Geology ABSTRACT Combination of a home-made thermoanalytical device (Derivatograph, MOM) and a quadrupole mass spectrometer (QMS-D, ATOMKI) is presented, and the simultaneous thermoanalytical method (DTA, DTG, TG, QMS-EGA) has been successfully applied in many fields of mineralogy, petrology, geochemistry and chemostratigraphy. In Hungary, positive experience has been obtained in the following fields: — determination of rare mineral in the Carpathian Basin. — Diagenetic and hydrothermal processes and facies were characterized by distinguished mineral associations in Hungary and Cuba. — Geological dating by investigations of sporadic finds (bones) of Neogene vertebrates. INTRODUCTION The most important information on various evolved gas analytic methods, such as mass spectrometry, gas chromatography, infra-red absorption, selective sorption and thermogas titrimetry will be found in the books and in the well-known journals and monographs. The Proceedings of the ICTA and ESTA provide an up-to-date picture of the stage of development of M S and G C - M S coupling system and their applications (e.g. B R A C E W E L L and R O B E R T S O N 1 9 8 0 ; F R I P I A T 1 9 8 2 ; M O R G A N 1 9 7 7 ; M Ü L L E R — V O N M O O S a n d M Ü L L E R 1 9 7 4 ; P A U L I K a n d P A U L I K 1 9 8 1 ; S Z É K E L Y et al. 1 9 8 0 ; W A R N E et al. 1 9 8 5 ) . The new method was used parallelly with thermogas titrimetry (TGT) and IR, GC, X-ray analyses to determine composition of the inorganic and organic com-pounds, minerals, rocks, building and raw materials, and has been successfully applied in many fields of chemistry and geochemistry ( D É V A I et al. 1984; K O Z Á K et al. 1 9 8 5 ; S Z Ö Ő R et al. 1 9 8 4 ; S Z Ö Ő R a n d B O H Á T K A 1 9 8 5 ; S Z Ö Ő R a n d B A L Á Z S 1988). A few examples demonstrate that simultaneous technique is very helpful and it is basic method for wide area of experience. * H—4010 Debrecen, P.O.Box. 4. Hungary 57 INSTRUMENT AND METHOD A home-made quadrupole mass spectometer (BERECZ et al. 1983) has been coupled to the Derivatograph and got a versatile instrument promising the possi-bility of a fast, sensitive evolved gas analysis (Fig. 1.). MOLECULAR FILTER FURNACE I FLUSHING ™ I GAS RECORDER VACUUM SYSTEM S J p ( 0 CAPILLARY F g j T PU*® BALARE c±±i BALARE SA№UNG UMff DERIVATOGRAPH 6UADRUP0LE MS SYSTEM Fig. 1. Schematic drawing of the Derivatograph (MOM) and QMS-D (ATOMKI) system The quadrupole mass spectrometer has a mass range of 1-300 a.m.u. and a sensitivity of 4 1 0 - 4 A/mbar with Faraday cup. It is mounted on a bakeable high vacuum system consisting of a liquid nitrogen cooled refrigerator, water cooled oil trap and oil diffusion pump. Ultimate pressure is less than 1-10~° mbar without baking. Gases are pumped from the reaction chamber through a 1.2 m long capillary and a small portion of the sample is introduced into the quadrupole via a molecular filter at the low-pressure end of the capillary. The tip of capillary is 2 cm below the sample holder. The coupling unit can be heated up to 200 °C, its gas consumption is about 0.5 cm3/s, response time is 50 ms but this latter is not exploited because of the large volume of the reaction chamber ( -50 cm3). The response time of the whole coupled system is 20 s at 3 cm3/s air flow rate. This is satisfactory as the fastest heating program of the Derivatograph is 20 °C/min. Sensitivity: during the thermoanalysis is 1 mg Ca(COO)2 • H2O, the signal at the output of the quadrupole is 50 times higher than the noise amplitude. The volatile components are identified on the basis of the complete mass-spectra, while the changes in each component of given mass are monitored as a function of temperature with the aid if a peak selector. The measurements were performed under the following conditions: tempera-ture range 1000 °C; rate of heating: 10 °C /minute in helium or air current; sample holder: platinum or ceramic crucibles. The interpretation of calcium oxalate monohydrate (whewellite) an example of our first investigations (Fig. 2). The decomposition processes take places as follow in helium atmosphere. Ca(COO)2 • H2O = Ca(COO)2 + H2O 210 °C (1) Ca(COO)2 =CaCQ3 + CO 510 °C (2) 58 2CO = CO2 + C CaC03 = CaO + CO2 CaC03 + C = CaO + 2 CO The processes are different in air atmosphere. 820 °C (3) 600 woorti Fig. 2. The thermal decomposition of whewellite RESULTS AND DISCUSSIONS The examples reported in this paper demonstrate that simultaneous technique is a very helpful means in the characterization of geological materials. Mellite, hydrate aluminium mellate, Al2[Ci20i2]- 18 or 16 (?) H2O is a very rare mineral, it is unique in the Carpathian Basin (Csordakut, Hungary). The crystal water content of mellite was controversial up to the present. The Fig. 3. shows the loss of water in the first endothermic process, it is 39.73 %, - 1 6 moles in the formula (SZOOR and BOHATKA 1985). Fig. 3. The thermal decomposition of mellite 9 59 A Lower Pannonian (Miocene) gravel complex is cemented by marcasite deposited by low temperature hydrothermal activity ( V I C Z I A N et al. 1986). In this locality the light yellow incrustration on the weathered rock surface were hydrous iron sulphate minerals. The X-ray diffraction indicated the minerals as copiapite, (Fe2+,Mg)Fe43+[(OH)(S04)3]2'20H20 and rhomboclase, Fe3+H[SC>4]2 • 4H2O. The combined thermoanalytical investigations showed H2O and SO2 as main components, minor amounts of S and CO2 indicated impurities in the evolved gases {.Fig. 4.). The percentages of the hydrous sulphate minerals are copiapite: 54 percent, rhomboclase: 23 percent as computed considering the weight loss of H2O and SO3 from the total sample. The remaining 23 percent is mainly amorphous SiC>2. This method was used to determine silicate, carbonate, hydroxide mineral paragenesis of ultramafic rocks (peridotite, serpentinite). According to the water and carbon dioxide detected to antigorite, chrysotile, brucite and magnezito-calcite were identified (Fig. 5.). The mass spectrometry combined with Derivatograph can reveal the presence of various carbonates, sulphates, clay minerals in raw and building materials. Fig. 6. shows two typical examples. At the foreground of North Borsod Karst, Hungary, there are some shallow boreholes, which have organic material bearing layers in the Upper Pannonian ingression lagoon sediments. Two characteristic diagenetic processes and facies 60 A. B. C. D. Fig. 5. Mineral paragenesis of serpentinite, from Bogoslovac, Yugoslavia (A), Trodos, Cyprus (B), Bodvarako, Hungary (C) and Tacajo, Cuba (D) a=antigorite, ch=chrysotile, b=brucite, m=magnesito-calcite 61 D T G dm/dt mg/minl HOH* . . . CO2 SOj (»1001 1000CCI 1000 I'C ] Fig. 6. Mineral paragenesis of a brick clay from Great Hungarian Plain (A) and an important tuffigene raw material, beidellite from Banes, Cuba (B) a=amorphous material, c=calcite, d=dioctahedral smectite, g=goethite, m=mirabilite, s=interstratified mica-smectite, o=organic material were distinguished by DTA, DTG, TG, QMS-EGA, GC, IR and Rock Eval pyrolysis methods (SZOOR et al. 1986). In the siderite facies, the organic materials was disintegrated under oxidative circumstances, while in the case of calcite and gel pyrite facies, typical aliphatic protobitumens accumulated in a reductive environment (Fig. 7.). A new geochronological method has been developed by the authors ( S Z O O R , 1982a,b; S Z O 6 R et al. 1987). The evaluation of the DTA, DTG, TG curves of Quaternary vertebrate fossil materials produced characteristic parameters closely related to geological age. Using this statement as a means for dating carried out a chronostratigraphic evaluation. In this paper we demonstrate the mass spectrometric thermal analysis which provided the required information to explain the difference in the composition of fossil bones by measuring the evolved gases. In the course of our work this chronological well-defined sporadic find was evaluated. The first data is 20100 years, the other one is 100000 years. Fig. 8. shows the results of examinations. Water as basic constituent was released up to 220 °C from the organic and inorganic structures (A process). In this range carbon dioxide relates to the beginning of the decomposition of fossile collagen. The main process B takes place between 220 and 600 °C. The quantity and MS-pattern of organic gas components are different in samples of different ages. The carbonate of apatite and calcite secondarily built into the structure dissociated in the range of 600—1000 °C (C process). In the future it will be completed to reveal the regularities of collagene with check by GC-MS analyses. 62 390 *C ' E g jd r* i/l I £ O n- , 1 \ Li 4li Fig. 7. DTA, DTG, TG, QMS-EGA analysis of argillaceous aleurite ("oil shale")from Teresztenye, Hungary. H2O, CO2, H2S, mass number (M) 41 and 55 were continuously detected, complete mass spectrum at 390 °C (in He-atmosphere with some air-contamination) 63 I II. Fig. 8. DTA, DTG, TG, QMS-EGA analysis of sporadic finds (bones) 1=20000 and D.= 100000 years old (B.P.) R E F E R E N C E S BERECZ, I., S. BOHÁTKA, G. LANGER and G. SzööR, 1983: Quadrupole mass spectrometer coupled to derivatograph. — International Journal of Mass Spectrometry and Ion Physics. 47, pp. 273— 2 7 6 . BRACEWELL, I. M. and G. W. ROBERTSON, 1980: Pyrolysis-mass spectrometry studies of humifica-tion in a peat and a peaty podzol. — J. Anal. Appl. Pyrol. 2, pp. 53—62. DÉVAI, I., C . HEIM, I. WITTNER, G . DÉVAI, Z. DINYA, J. HARANGI, G. SZÖÖR and F. MÁTÉ, 1 9 8 4 : Detection of Elementary Sulphur in Freshwater Sediments. — Environmental Pollution (Ser. B) 8. 2, pp. 155—160. FRIPIAT, J. J., 1982: Advanced Techniques for Clay Minerals Analysis. — Elsevier KOZÁK, M., I. BARTA, G. SZÖÖR, 1985: Mineralogical and geochemical investigation of the halloysite from Kővágóörs (Keszthely Mountain, W-Hungary) and its genetics. — Földtani Közlöny, 115, 3. pp. 281—292. MORGAN, D. J., 1977: Simultaneous DTA-EGA of minerals and natural mineral mixtures. — J. Therm. Anal. 12, pp. 245—263. MOLLER-VONMOOS, M., R. MÜLLER, 1974: Application of DTA-TG-MS in the Investigation of Clays. — Thermal Analysis, 4th ICTA (Edited by I. Búzás) 2, p. 521. PAULIK, J. and F. PAULIK, 1981: Simultaneous Thermoanalytical Examination by means of the Derivatograph. — Elsevier SZÉKELY, T., F. TILL and G. VÁRHEGYI, 1980: Characterization of Fossil Fuels by Computer Aided Thermobalance-Mass-Spectrometer System. — Thermal Analysis, 6th ICTA (Edited by W. Hemminger) 2, pp. 365—371. SzööR G., 1982a: Fossil age determination by thermal analysis. — J. Therm. Anal. 23, pp. 81—83. SzööR G., 1982b: Geological dating by thermal analysis. — Thermal Analysis, 7th ICTA (Edited by B. Miller) 2, pp. 1463—1469. SzööR G., E. BALÁZS, S. BOHATKA, 1984: Joint Determination of Clay Minerals, Carbonates and Sulphates by complex Thermoanalytical Method. — Építőanyag. 9, pp. 274—277. (in Hunga-rian) 64 SzöÓR G., M. HETÉNYL, É. BALÁZS, S. BOHATKA, 1986: Geochemical facies analysis of the typical organic material bearing Pannonian layers at the foreground of North Borsod Karst (Hungary). Földtani Közlöny. 116-2. pp. 137—146. (in Hungarian) SzöÓR, G. and S. BOHÁTKA, 1985: Derivatograph-QMS system in Geochemical Research. — Thermochim. Acta. 92, pp. 395—398. SzöÓR, G., S. BOHÁTKA, L. KORDOS, 1987: Investigation of quaternary sporadic finds (Vertebrata) by DTA, DTG, TG, QMS-EGA method. — Pleistocene Environment in Hungary (Edited by M. Pécsi). Hungarian Academy of Sciences. Budapest, pp. 227—231. SzöÓR, G., É. BALÁZS, 1988: Mineral Efflorescence on the Surface of Walling Bricks from the Mezőtúr Factory. Építőanyag. 6, pp. 217—222. (in Hungarian) VicziÁN, I., M. KOZÁK, G. SzöÓR, 1986: Marcasite, copiapite and rhomboclase in Lower Pannonian gravels at Uzsa (Central Transdanubia). — MÁFI Évi Jelentése, pp. 377—387. (in Hungarian) WARNE, S . S . J., A . J. BLOODWORTH, D . J. MORGAN, 1 9 8 5 : T h e r m o m a g n e t o m e t r y and e v o l v e d g a s analysis in the identification of organic and pyritic sulphur in coal and oil shale. — Thermal Analysis, 8th ICTA (Edited by A. Blazek) 2, pp. 745-748. Manuscript received, 13 November, 1990 65 

An apparatus for simultaneous thermal analysis and its applications in geological research

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An apparatus for simultaneous thermal analysis and its applications in geological research

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