th 57 Annual Meeting of the International Committee for Coal and Organic Petrology – ICCP
A B S T R A C T S
18-23rd September 2005 Patras, Greece
Organizing Committee Assoc. Prof. Dr. Kimon Christanis, University of Patras Prof. Dr. Prodromos Antoniadis, National Technical University of Athens Prof. Dr. Andreas Georgakopoulos, University of Thessaloniki Dr. Cassiani Papanicolaou, Institute of Geology and Mineral Resources Dr. Stefanos Papazisimou, University of Patras Dr. Antonis Bouzinos, University of Patras Mr. Stavros Kalaitzidis, Ph.D. student, University of Patras
Contents
VASCONCELOS L., SIQUELA E. Variation of rank of World coals with age 7
JELONEK I., KRUSZEWSKA K., FILIPIAK P. Liptinite as an indicator of environ- 8 mental changes during coal seam formation as based on the seam no 207 profile (Upper Silesia, Poland)
ZDRAVKOV A., KOSTOVA I., KORTENSKI J. Coal properties and depositional 9 environment of the Neogene Elhovo lignite, Bulgaria
HACKLEY P., MARTÍNEZ M. Organic petrology of Paleocene Marcelina 10 formation coals, Paso Diablo Mine, Western Venezuela
İNANER H., NAKOMAN E. Properties of lignite deposits in western Turkey 11
KARAYIĞIT A.I. Petrography and facies analysis of the Miocene Soma coals, 12 Manisa-Turkey
NADER E., OPLUŠTIL S., SÝKOROVÁ I. Coal Facies and depositional environ- 13 ments of the 9th and 10th overlying coals of the Žacléř group (Duck- mantian, Intra-Sudetic Basin, Czech Republic)
MAVRIDOU E., OIKONOMOPOULOS I., ANTONIADIS P. Reflectivity Measure- 14 ments in Lignite Deposits from Ptolemais Region (N. Greece)
PAPAZISIMOU S., KALAITZIDIS S., CHATZIAPOSTOLOU A., SIAVALAS G., 15 CHRISTANIS K., VAGIAS, D. Coal-petrographic characteristics of the Pellana lignites (cores KP7 and KP13), Lakonia, Greece
CUKALLA M., SERJANI A. Coals of Albania and new aspects of development 16
STEFANOVA M., MARINOV S.P., STAMENOVA V., GONSALVESH L., ZDRAVKOV 17 A. Preliminary observation on biomarker composition of Neogene Lom lignite, Bulgaria
KOSTOVA I., ZDRAVKOV A. Organic petrology and mineralogy of coals from 18 Maritza-West Basin, Bulgaria
PRONINA N.V., FADEEVA N.P. Different types of organic matter from Anadyr 19 basin (North-East Russia)
SÝKOROVÁ I., MACHOVIČ V., MIZERA J., HAVELCOVÁ M., VAŠÍČEK M. 20 Petrological and geochemical characteristics of peat from the Krásno peat bog, Czech Republic
ŽIVOTIĆ D., LORENZ H., GRZETIĆ I., ERCEGOVAC M., SIMIĆ V. Some geoche- 21 mical characteristics of Soko Banja low rank coal, Eastern Serbia
VARMA A.K., MISHRA S. Geological and petrographic characterisation for pho- 22 sphorous distribution in some coal seams of Jharia coalfield, Jharkhand, India
3 KALKREUTH W., WILLETT J., FINKELMAN R., BURGER H., HOLZ M., KERN M., 23 MACHADO G., MEXIAS A., SILVA M. Petrology, chemistry and statistical evaluation of major and trace element distribution in Permian Coals from the Paraná Basin: Santa Terezinha, Leão-Butiá and Candiota Coalfields, Rio Grande do Sul, Brazil
HÁMOR-VIDÓ M., HÁMOR T. Petrography and isotope geochemistry of Hunga- 24 rian power supply coals
GOODARZI F. Can mercury be reduced in feed coal and stack emission? Role of 25 organic matter - A Canadian example
RASULOV A. Compositional differences in diagenetic carbonates from coal- 26 bearing deposits of the Pechora Basin, Russia
HÁMOR-VIDÓ M., CSERNY T., KUTI L. Tracing anthropogenic impacts in 27 association with environmental changes in Lake Balaton sediments using organic petrology
STUKALOVA I.E., RUSINOVA O.V. Thermal alteration of coals in the Khasyn 28 coalfield (Magadan Region, Russia)
MORGA R., KOMOREK J. Internal structure of thermally altered vitrinite in the 29 view of FTIR and Raman spectroscopy examination
KOMOREK J., MORGA R. Optical properties of sporinite and semifusinite 30 subjected to thermal treatment
SANEI H., STASIUK L.D., GOODARZI F. Organic petrology of recent lacustrine 31 sediments during thermal alteration by Rock-Eval Pyrolysis
MISZ M., FABIAŃSKA M., ĆMIEL S. Petrographic and chromatographic 32 investigations on organic components in thermally altered coal waste
STEFANOVA M. Pyrolytic behavior of some Thracian lignite lithotypes, Bulgaria 33
PROBIERZ K., MARCISZ M. Changes in the quality of coal - From in-situ coal 34 through processing, to commercial coal
MISZ M., SÝKOROVÁ I., MACHOVIČ V. Slag and fly ash deriving from the 35 combustion of lignite in PF boilers at the Bełchatów Power Station (Poland)
ALVAREZ D., FERNÁNDEZ DOMINGUEZ I., BORREGO A.G. Coal combustion 36 under oxy-fuel conditions. Comparison of the petrographic characteristics of coal chars obtained under O2/N2 and O2/CO2 atmospheres
STOJILJKOVIĆ D., ERCEGOVAC M., RADOVANOVIĆ M. Micropetrographic 37 characteristics of the char types from low rank coal combustion of Serbia
ERCEGOVAC M., ALEKSIC B.R., CVETKOVIC O.G., ALEKSIC B.D., ŽIVOTIĆ D., 38 VITOROVIC D. Micropetrographic characteristics of solid residues after catalytic hydrogenation of the Serbian low rank coals
4 MASTALERZ M., DROBNIAK A., RUPP J., STRAPOC D. Influence of petrographic 39 composition of coal on desorption and adsorption capacity of carbon dioxide and methane; Examples from Indiana, USA
PREDEANU G., PANAITESCU C. Non-conventional method to determine the 40 structure of the activated carbon
PANAITESCU C., PREDEANU G. Research on microstructural characteristics of the 41 TI and QI from the coal tar, coal pitch and their cokes
KWIECIŃSKA B., PUSZ S., KRZESIŃSKA M., PILAWA B. Physical studies of 42 shungite
RANASINGHE P., COOK A.C. Combining petrological and chemical approaches to 43 source rock evaluation - a follow up on an early study
KERN M., PACHECO R., ENGELKE V., KALKREUTH W., MACHADO G., MEXIAS 44 A., VARGAS T., COSTA J. Geochemical and petrographical characterization of black shales from Irati and Ponta Grossa formations, Paraná Basin, Brazil
NOWAK G.J. Microscopic identification, classification and comparison of organic 45 matter composition of the Late Palaeozoic black shales of SW Poland
AVRAMIDIS P., ZELILIDIS A. Organic geochemistry, potential source rocks and 46 thermal maturation in southern depocenter (Kipourio – Grevena) of Mesohellenic Basin, Central Greece
NOWAK G.J., GÓRECKA-NOWAK A., KWIECIŃSKA B. The research problems of 47 organic matter dispersed in the Carboniferous-Permian lacustrine black shales from the Sudetic Basins (SW Poland)
TROSKOT-ČORBIĆ T., ŠPANIĆ D., RUMENJAK LJ., MARIČIĆ M., STANKOVIĆ I. 48 Organic petrology and geochemistry of Jurassic carbonates of the Karst Dinarides (Croatia)
ŠPANIĆ D., TROSKOT-ČORBIĆ T., ČULJAK V., MARIČIĆ M., RUMENJAK LJ., 49 STANKOVIĆ I. Organic petrology and geochemistry of the Cretaceous carbonates of the Karst Dinarides (Croatia)
IORDANIDIS A., BUCKMAN J., TRIANTAFYLLOU A.G., ASVESTA A. Bioaerosols in 50 Kozani area, northern Greece as viewed by Environmental Scanning Electron Microscopy
AUTHOR INDEX 51
5
th Patras 2005: 57 Annual Meeting of the ICCP
VARIATION OF RANK OF WORLD COALS WITH AGE
Vasconcelos, L., Siquela, E.
Department of Geology, Eduardo Mondlane University, PO Box 257, Maputo, Mozambique ([email protected])
Temperature, pressure and time are the main causes for coalification. However, time is considered to have effect on coalification only when temperatures are sufficiently high to speed up chemical reactions, i.e., the higher the temperature, the greater the influence of time. The treatment of 5154 data on World coals from more than 150 coal basins and 145 coal fields carried out during this study shows that for coals of all Eras (Palaeozoic, Mesozoic and Cenozoic) and facies (Gondwana, North Atlantic) the dominant coal rank is bituminous, specially sub-bituminous, irrespective of the deposition and dynamo- thermal conditions. When particular periods and regions are considered, there are some exceptions to this general trend. For instance, Quaternary coals are dominated by peat. In South America Cenozoic coals are predominantly sub-bituminous, and in Gondwana Asia Cenozoic coals are mainly lignites. European coals of Mesozoic and Cenozoic ages are mainly sub-bituminous, although Cenozoic bituminous coals occur almost with the same frequency as the sub-bituminous coals. The amount of heat necessary to provoke coalification up to the bituminous stage is relatively low. On the other hand, during this stage, organic matter deposits are characterized by high fluid contents and by H-bonds in the molecular structures of their components. Both fluids and H-bonds give the system a greater thermal conductivity and heat circulation efficiency, as well as a greater penetrability throughout the basin, allowing thus an “easy” coalification up to the bituminous stage. At this stage, coal goes through a chemical stability due to the loss of the above mentioned properties. Heat circulation faces a resistance justified by the enrichment of carbon content, which is known to be thermo-isolator. The spatial distribution of heat varies gradually towards the heat source, the most significant heat-effects being near the source. Thence the tendency of anthracite to form near the heat sources but with a short extension as a consequence, as stated before, of the short distance reached by heat due to the poor thermal conductivity of coal in the bituminous stage, and to the chemical stability that characterizes this rank stage. In other words, it looks like coal faces a relatively dynamo-chemical and dynamo-thermal facility to reach the bituminous stage, and a strong resistance to go beyond this stage. Being so, great amount of coals will stay in the range of bituminous coals.
7 th Patras 2005: 57 Annual Meeting of the ICCP
LIPTINITE AS AN INDICATOR OF ENVIRONMENTAL CHANGES DURING COAL SEAM FORMATION AS BASED ON THE SEAM No 207 PROFILE (UPPER SILESIA, POLAND)
Jelonek, I.., Kruszewska, K., Filipiak, P.
Faculty of Earth Sciences, University of Silesia, Będzińska 60, 41-200 Sosnowiec, Poland ([email protected])
Coal seam No 207 belongs to the Krakow sandstone series (Westphalian C) sediments of the Upper Silesia Coal Basin (Poland). According to its reflectance value (approximately 0.41% Rr or less), carbon content (daf) (approx. 71%) and calorific value (23–26 MJ), the discussed coal could be defined as transitional between low (subbituminous) and medium rank (bituminous), according to the International ECE Coal Classification. Macroscopically the profile shows general domination of vitrain and vitrous clarain in the lower part of the seam with the exception of the sapropelic layer, which occurs between two shale layers. The upper part of the seam is marked by the presence of tonstein layer. Above tonstein horizon up to the roof of the seam, the durain and dull clarain become frequent. In order to assess the liptinite occurrence and distribution throughout the seam profile, the following analyses have been carried out on 25 polished blocks representing the succession of samples taken from the bottom, up to the roof of the seam: maceral (under white reflected light and blue excitation) and microlithotype analyses, as well as random reflectance measurements. In addition the miospore assemblages were analysed in the transmitted light. The quantitative distribution of the liptinite as a group shows a high contribution (21–22%) in the lowest part of the seam up to the lower shale layer, and even higher (25%) immediately above it. The sample just below the higher shale level contains 45% liptinite and reveals typical sapropelic (cannel) features. Above the shale, up to the tonstein layer the liptinite content varies between 11% and 26%. Above the tonstein level only one sample has reached the value of 19%. The rest of samples up to the seam roof comprises 6–14% of liptinite. Among the individual macerals, macro- and microsporinite have followed the same pattern of distribution, whereas cutinite and resinite drop rapidly in frequency at the middle of the seam. Exsudatinite shows an irregular pattern of distribution and occurs in small portions (0.07–1.2%) throughout the whole profile. Liptodetrinite is distributed more or less evenly (3–7%), with the exception for the sapropelic layer where it reaches 10%. Alginite is scarce below the tonstein level (< 0.3%) and practically disappears above it. Miospore assemblages are generally dominated by Densosporites sp., which between shale layers is equally associated with Laevigatosporites sp. and Florinites sp. The latter ones dominate in the coal immediately above the upper shale layer. Above the tonstein level up to the roof of the seam the sequence is dominated by Densosporites, with other species occurring in traces or being absent. The results of both petrographic and palynological analyses show that liptinite within the seam profile has been affected in accordance to environmental changes.
8 th Patras 2005: 57 Annual Meeting of the ICCP
COAL PROPERTIES AND DEPOSITIONAL ENVIRONMENT OF THE NEOGENE ELHOVO LIGNITE, BULGARIA
Zdravkov, A.1, Kostova, I.2, Kortenski, J.1
1 Department of Economic Geology, University of Mining and Geology “St. Ivan Rilski”, 1700 Sofia, Bulgaria ([email protected]) 2 Sofia University “St. Kliment Ohridski”, 1000 Sofia, Bulgaria
Coal petrological investigations, along with proximate analyses were performed, in order to determine the depositional environment of the Elhovo coal. Forty-five samples were collected from three boreholes in the eastern part of the basin. The Elhovo lignite formed during the transgressive stage of a tectonic graben, located near the southern margin of the Bulgarian sector of the Alpine Mountain chain. It is an intra-orogenic extensional structure, formed during the final stage of the Alpine orogeny. Several coaly layers formed during the transition from a fluvio-deltaic to a lacustrine environment, but only three of them, 2 to 8 m thick, are considered (sub-) economic. The coal is characterized by high ash yields and sulphur contents. It formed in a rheotrophic, low-lying fresh water mire with high pH value. Despite of the alkaline environment the bacterial activity was limited and the tissue preservation and gelification were mainly controlled by the wet/dry conditions. The high sulphur contents (up to 15%) are interpreted as a result of the influence of sulphate-rich waters, passing through numerous mineralized zones and ore deposits, located within the catchments area. During peat accumulation areas with open water were absent. Each peat-forming stage commenced after a sharp drop of the water table and ended with a rapid increase of the water level. Vegetation, rich in decay resistant conifers, dominated in the Elhovo basin. The coal in drillholes 122 and 145 deposited under relatively dry conditions, whereas to the south a flooded forest swamp (drillhole 104) formed. Despite of the dry conditions the thermal destruction was very limited. Coal formation processed in an environment, characterized by low subsidence rate, in which prior to the burial the woods were subjected to severe mechanical destruction. Due to the enhanced impregnation of the tissues, bacteria and fungi played only secondary role in the process of humification. Peat accumulation was terminated by a major flooding event and the short term establishment of a lake.
9 th Patras 2005: 57 Annual Meeting of the ICCP
ORGANIC PETROLOGY OF PALEOCENE MARCELINA FORMATION COALS, PASO DIABLO MINE, WESTERN VENEZUELA
Hackley, P.1, Martínez, M.2
1 U.S. Geological Survey, MS 956 National Center, Reston VA 20192, USA ([email protected]) 2 Instituto de Ciencias de la Tierra, Facultad de Ciencias, Universidad Central de Venezuela. Apartado Postal 3895, Caracas 1010 A, Venezuela
About 7 Mt of high-volatile bituminous coal is produced annually from four coal zones of the Upper Paleocene Marcelina Formation at the Paso Diablo open-pit mine of western Venezuela. As part of an ongoing coal quality study, we have characterized the organic petrology of twenty-two coal channel samples from Paso Diablo. Samples also were analyzed for proximate-ultimate, and calorific values. Ash yield is low, averaging 1.9 wt.-%, dry (range 0.4-14.3 wt.-%); sulfur content is similarly low, at avg. 0.7 wt.-%, dry (0.4-1.4 wt.-%). Calorific value averages 33.66 MJ/kg m,mmf (32.33-34.66 MJ/kg), consistent with the rank classification determined by vitrinite reflectance (Rmax 0.65- 0.78). Vitrinite content averages 79 vol.-% (67-97 vol.-%); avg. inertinite content is 19 vol.-% (2-33 vol.-%). Liptinite constitutes 2 vol.-% on avg. (0-3.4 vol.-%). Six of the samples represent incremental benches across the No. 4 bed, the stratigraphically lowest mined coal, which also is mined at the 10 km distant Minas Norte open-pit. Organic content of the No. 4 bed indicates an upward increase of woody vegetation and/or greater preservation of organic material throughout the life of the original mire(s). An upward increase in telovitrinite and corresponding decrease in detrovitrinite and inertinite illustrate this trend. In contrast, stratigraphically higher coal groups generally exhibit a ‘dulling upward’ trend. The generally high inertinite content, and low ash yield and sulfur content, suggest the Paso Diablo coals were deposited in rain-fed raised mires, protected from clastic input and subjected to frequent oxidation and/or moisture stress. However, the two thinnest coal beds (both 0.7 m thick) examined herein are each characterized by lower inertinite and higher telovitrinite contents relative to the rest of Paso Diablo coal beds, indicative of less well-established raised mire environments prior to drowning. Paleocene coals of western Venezuela, including the Paso Diablo deposit and correlative coal deposits of the Andes, are characterized by high inertinite and consistently low ash and sulfur content relative to Eocene and younger coals of the area. We interpret these age-delimited coal quality characteristics to be due to the tectonic control of subsidence rate. Slower subsidence rates dominated the Paleocene, while greater subsidence rates during the Eocene-Miocene resulted from the rapid emplacement of thrust sheets during the main construction phase of the Andean orogen. Slower subsidence in the Paleocene may have favored the growth of raised mires, generating higher inertinite concentrations through more frequent moisture stress. Consistently low ash yield and sulfur content would be due to protection from clastic input, in addition to the leaching of mineral matter by rainfall and the development of acidic conditions preventing fixation of sulfur.
10 th Patras 2005: 57 Annual Meeting of the ICCP
PROPERTIES OF LIGNITE DEPOSITS IN WESTERN TURKEY
İnaner, H., Nakoman, E.
Dokuz Eylül University, Faculty of Engineering, Department of Geological Engineering, 35100 Bornova, İzmir, Turkey ([email protected])
The total lignite reserves of Turkey are estimated to be 8.4 billion tonnes. The western Turkey coal formations constitute the most important reserves together with the Elbistan deposit (eastern Turkey) displaying proven reserves of 3.2 billion tonnes. Total lignite reserves in western Turkey are about 2.551 billion tonnes taking into consideration only the deposits with more than 10 million tonnes. They represent 33% of the total Turkish reserves and have been explored and evaluated by the General Directorate of Mineral Research and Exploration. They are currently exploited by the Turkish Coal Enterprises and some private companies using various mining methods. Coal exploration is still carried out in many fields of the region holding geological mapping and drillings. Lignite deposits of western Turkey are generally Miocene in age and are scattered in the region. They deposited in a limnic environment and display large reserves. The lignite- bearing formations lay unconformably over the Palaeozoic and Mesozoic basement. Lignite seams are underlain by arenaceous conglomerates, sandstones, sands and silts, and are overlain by cyclic deposited sediments such as marls, limestones, tuffites and alluvial sediments. Although the lignite quality strongly varies in the region (between 1335 kcal/kg and 4500 kcal/kg), the Miocene deposits have generally good quality. Tectonics has affected some of them. The deposits include up to three lignite seams having thicknesses between 5-10 m and mostly are mined in open pits. Most of the known lignite deposits in Turkey display low calorific values, high ash yields, high sulphur contents and high moisture. Generally, in the important lignite deposits of Turkey the total sulphur content varies between 0.50% and 6.51%. Almost 80% of the total reserves have calorific values below 2500 kcal/kg. The most important lignite deposits are situated in the regions of Manisa, Mugla, Kutahya, Bursa, Canakkale, Balikesir and Aydin provinces of Western Turkey. Nowadays, the exploited lignites are used in industry, for domestic heating and power generation. The power plants of Soma (Manisa), Tuncbilek and Seyitomer (Kutahya), Yatagan, Yenikoy and Kemerkoy (Mugla), Orhaneli (Bursa) and Can (Canakkale) are fed with lignites exploited from nearby mines. Taking into consideration the fact that Turkish lignites are used in power plants, have low calorific values, high sulphur and ash contents, further research is needed in order to minimize the environmental impact.
11 th Patras 2005: 57 Annual Meeting of the ICCP
PETROGRAPHY AND FACIES ANALYSIS OF THE MIOCENE SOMA COALS, MANISA-TURKEY
Karayiğit, A.I.
Hacettepe University, Department of Geological Engineering,06532, Beytepe-Ankara, Turkey ([email protected])
The Soma basin, which is one of the most productive lacustrine coal basins of western Anatolia-Turkey, contains three coal seams of Miocene age, lower (kM1-2), middle (kM3), and upper (kP1-2). The lower and upper seams are currently exploited in underground and mainly open-cast mines, but not the middle. The lower and middle seams are located in the Soma Formation and the upper seam in the Denis Formation. The basin has a coal reserve of 660 Mt. A run-of-mine coal production of approximately 11 Mt a year is consumed for domestic heating due to relatively low-sulfur content and high calorific value, and also feeds the coal-fired Soma power plant. The purpose of this study was to investigate mineralogy, petrography and facies conditions of the Soma coals. The results of proximate analysis show that the ash yields of the Soma coals have a wide range, in which ash yields are higher in the coal samples from the kP1-2 seam in the Denis coal fıeld. Kaolinite is the abundant mineral of altered pyroclastic materials, which are identified in kM1-2 seam in the Eynez and Isıklar coal fields. In addition, alkali feldspar (sanidine?), chlorapatite and zircon have been also determined. These materials indicate contemporaneous volcanic input during peat formation. This study implies that volcanic inputs during peat formation in the kM1-2 seam are decreasing from southwestern part (Eynez) to the northeastern part (Denis) of the coal basin. Maceral analysis shows that kM1-2 seam includes higher huminite contents, whereas kM-3 and especially kP1-2 seams are enriched in mineral matter. Indices of TPI and GI indicate that kM1-2 seam in Eynez, Isiklar and Denis generally shows clear differences from kM-3 seam in Isiklar and kP1-2 seam in Denis. Mean values of random huminite reflectance measurements (%Rr) of the coals from kM1-2 seam are found as 0.45% Rr in Eynez, 0.43% Rr in Isiklar, and 0.38% Rr in Denis. This indicates that coal rank in kM1-2 seam slightly decreases from Eynez to the Denis coal fields. Mean values of %Rr of the coals from kM-3 seam in Isiklar and kP1-2 seam in Denis are found as 0.46% Rr and 0.40% Rr, respectively. Mean values of random huminite reflectance of the coals indicate that coal rank can be classified as “subbituminous B” for the Eynez and Isiklar coals and “subbituminous C” for the Denis coals.
12 th Patras 2005: 57 Annual Meeting of the ICCP
COAL FACIES AND DEPOSITIONAL ENVIRONMENTS OF THE 9th AND 10th OVERLYING COALS OF THE ŽACLÉŘ GROUP (DUCKMANTIAN, INTRA-SUDETIC BASIN, CZECH REPUBLIC)
Nader, E.1, Opluštil, S.1, Sýkorová, I.2
1 Faculty of Science, Charles University, Albertov 6, 128 43 Prague 2, Czech Republic 2 Institute of Rock Structure and Mechanics, Academy of Science of the Czech Republic ([email protected])
Two currently exploited coal seams of the Žacléř group in the Intra-Sudetic Basin have been studied petrographically and geochemically in order to reconstruct their sedimentary environment and hydrological development. The Intra-Sudetic Basin, situated along the Czech-Polish border, represents intra-continental basin filled dominantly with fluvio-lacustrine sedimentary rocks of Mississippian to Triassic age. Coal seams nos. 9 and 10 of the overlying subgroup (Duckmantian) merged in a single coal seam were selected for rank estimation, petrographic and petrologic analyses. Analyses were performed on 34 samples, which represent in total a coal thickness of 347.5 cm within a 740 cm thick seam. The atomic H/C - O/C ratio diagrams show that most of the coal samples followed mainly the vitrinitisation path being situated within the mature zone of catagenesis. Vitrinite reflectance, calorific value, moisture, volatile matter and carbon contents indicate a high-volatile bituminous B rank. Maceral analyses revealed the predominance of macerals of the vitrinite group (45-81%), followed by inertinite (8-34%) and liptinite macerals (10-28%). Coal is dominated by duroclarain (62.1%), whereas other lithotypes are less common: durain (18.7%), clarain (9.2%), clarodurain (3.5%), vitrain (2.6%) and fusain (1.9%). Presence of thick vitrite bands (between 10 mm up to 40 mm thickness) in coal seam confirms the existence of arborescent plants within the former mire. Average ash and sulfur contents are 17.26% (db) and 1.8% (db), respectively. These values refer to rheotrophic mire. Collotelinite reflectance of the studied profile reveals cyclic oscillation interpreted in term of redox potential changes due to water table fluctuation in former mire. Gelification and tissue preservation index diagram indicates peat deposition in telmatic environment in wet forest swamp of piedmont plain setting.
Acknowledgements: This study was financed through Grant No. IAA 300460510 by the Grant Agency of the Academy of Sciences of the Czech Republic.
13 th Patras 2005: 57 Annual Meeting of the ICCP
REFLECTIVITY MEASUREMENTS IN LIGNITE DEPOSITS FROM PTOLEMAIS REGION (N. GREECE)
Mavridou, E., Oikonomopoulos, I., Antoniadis, P.
National Technical University of Athens, Department of Mining Engineering, 9 Iroon Polytechniou Street, Athens 157 73, Greece ([email protected])
This poster presents the study of huminite reflectance on lignite samples coming from Ptolemais basin in Northern Greece. The elongated intermontane Florina-Ptolemais- Kozani basin is a NNW-SSE trending graben system that extends over a distance of 250 km from Bitola (F.Y.R.O.M.) to Servia, southeast of Kozani (GR). The basement consists of metamorphic schists in the west and crystalline limestone in the east. Lignite seams are of Neogene age and they are found alternating with marls and clays. All lignite deposits of the area were originally parts of a bigger unified lignite deposit and were later divided due to tectonic activity. Collected samples, which are coming from representative lignite seams from several lignite deposits, were studied under microscope in the past. At least 2 samples of each deposit were selected, while stratigraphic correlation between samples was one of the major selection criteria. Reflectance was counted on eu-ulminite macerals (A and B type). On each lignite sample, 100 individual determinations were conducted. The program mpv.exe, which was compatible with the coal petrographic microscope Orthoplan Leitz 307, was used for the measurements. Eu-ulminite reflectance of the samples was an indicator for the level of maturation of the individual samples, as well as of how lignite deposits evolved during peat-lignite formation.
14 th Patras 2005: 57 Annual Meeting of the ICCP
COAL-PETROGRAPHIC CHARACTERISTICS OF THE PELLANA LIGNITES (CORES KP7 AND KP13), LAKONIA, GREECE
Papazisimou, S.1, Kalaitzidis, S.1, Chatziapostolou, A.1, Siavalas, G.1, Christanis, K.1, Vagias, D.2
Department of Geology, University of Patras, GR-26500 Rio-Patras, Greece ([email protected])
The aim of this study is to determine the coal-petrographic features of the Pellana lignite, in order to assess the depositional palaeoenvironment and also to provide data useful for the exploitation and utilization of this deposit. Ash contents, as well as the contents of the elements C, H, N, O and S were determined in three lignite samples from core KP7 and eight samples from core KP13. Polished block sections from the same samples were examined under the microscope. The ash contents (at 750oC) of the studied lignite seams range among 14-72.5% (on dry basis). The contents of C, H, N and O (on dry basis) display values between 12.4-51.6%, 1.5- 4.0%, 0.2-1.2% and 11.2-27.5%, respectively. Sulphur contents do not exceed 0.7% in the three samples from core KP7, whereas in core KP13 sulphur ranges between 1.1- 4.8%. Huminite group dominates with values between 88.5-99 vol.-%, mmf. The studied samples display a distinct prevalence either in detrohuminite (up to 67 vol.-%, mmf) or in telohuminite maceral subgroup (up to 75.5 vol.-%, mmf). Liptinite and Inertinite maceral groups show low contents, which do not exceed 9% and 5%, respectively. The Pellana lignite is mainly medium to very low-grade. In terms of maturity the studied seams can be regarded as peat to lignite. Most of the lignite benches formed in fens under limnotelmatic conditions favourable for degradation. Tissue preservation depended either on the ratio of plant growth and peat accumulation versus rise of water table due to the subsidence rate and/or perhaps on the vegetation origin.
15 th Patras 2005: 57 Annual Meeting of the ICCP
COALS OF ALBANIA AND NEW ASPECTS OF DEVELOPMENT
Cukalla, M.1, Serjani, A.2
1 Mining and Processing Technology Institute, Blloku “Vasil Shanto”, Tirana, Albania 2 Geological Research Institute, Blloku “Vasil Shanto”, Tirana, Albania ([email protected])
To discuss again about coal it seems very strange, remembering that twenty years ago Albania was producing more than two million tonnes coal per year, while nowadays coal production is limited. In spite of that, in this paper a development program for coal exploration under the framework of the “Strategy of Mining Industry” is presented. In general, coal deposits of Albania are hosted within the molasse basins of Pre-Adriatic Depression (PAD), as well as in some inner depressions. Coal basins were formed in Oligocene-Lower Miocene, Tortonian (Upper Miocene), and Pliocene, while Maliqi peat is a Quaternary formation. The total coal reserves of Albania account for 794 million tonnes, which are distributed as follows: 86% are located in Tirana basin, 10% in Korça, Pogradeci and Kolonja basins, 4% in Memaliaj basin. In Maliqi (Korça region), 156,198,976 m3 peat reserves of gross calorific value 2200 kcal/kg are prospected. Commonly, Albanian coals are of lignite rank with gross calorific values ranging between 2000 and 5600 kcal/kg (average 3200-3300 kcal/kg). After benefication, gross calorific value in concentrate rises up to 4500-5500 kcal/kg. Before 1990, 20 mines were operating with a production capacity between 50,000 and 450,000 t/a. The coal exploitation in Albania was intensively carried out during the 1970’s and the 1980’s, reaching its maximum (2 Mt) in 1990. Based on the rank, two main groups are defined: coal and lignite. Mborje-Drenova and Homeshi deposits are of coal rank, whereas Memaliaj, Tirana and Gore-Mokrra deposits are of lignite rank. The new program of coal industry must be an intervention model of cooperation of Government with private sector, in order to create an economically and environmentally sustainable management system. Concrete projects should involve partners from the following markets and industries: environmental agencies, control equipment companies that apply new methods in power generation and clean-coal technologies.
Burning of coal through a zero-emissions system is possible at industrial scale. CO2 produced can be converted to a solid residue after reacting with an appropriate material such as serpentinites, which frequently occurs close to the coal basins. Deposits in Albania that are economically recommended are: Memaliaj (annual production 120,000 t/a, gross calorific value 4300 kcal/kg, cost 26 USD/t), Verdova- Dardhas (production 140,000 t/a, gross calorific value 2450 kcal/kg, cost 21 USD/t), Priske-Mushqeta (production 90,000 t/a, gross calorific value 3490 kcal/kg, 22 USD/t), Korça deposits (production 51,000 t/a, gross calorific value 2500 kcal/kg, cost 18 USD/t), Mborje-Drenova (production 20,000 t/a, gross calorific value 2690 kcal/kg, cost 18 USD/t), Maliqi peat deposit (production 2 million t, gross calorific value 2200 kcal/kg, cost 9 USD/t).
16 th Patras 2005: 57 Annual Meeting of the ICCP
PRELIMINARY OBSERVATION ON BIOMARKER COMPOSITION OF NEOGENE LOM LIGNITE, BULGARIA
Stefanova, M.1, Marinov, S.P.1, Stamenova, V.1, Gonsalvesh, L.1, Zdravkov, A.2
1 Institute of Organic Chemistry, Bulgarian Academy of Sciences, Acad. G. Bonchev Str., Block 9, 1113 Sofia, Bulgaria ([email protected]) 2 University of Mining and Geology “St. Ivan Rilski”, 1700 Sofia, Bulgaria
Only few publications regarding the geology and coal petrology of the Lom lignite are available, whereas organic geochemical investigations lack so far. The lignite from the Lom basin is the only coal of Pliocene age found in Northern Bulgaria. The coal formation occurred near the southern margin of the Dacian basin, where a vast delta plain formed. A northward migration of the alluvial-deltaic facies was established. In such environment extensive peat accumulation took place and resulted in the deposition of up to 40 m thick low rank coal seam interfingering with layers and lenses of unsorted sands, sandy clays and clays. Our study is the first attempt to characterize biomarker assemblage of the Lom lignites with the aim to confirm, reject concepts or just enrich our knowledge for this basin. The micropetrographic composition of Lom lignite is dominated by an attrinitic groundmass (up to 85 vol.-%, mmf) containing small amounts of corpohuminite (< 1 vol.-%, mmf); microsporinite (1-1.5 vol.-%, mmf); cutinite (< 1 vol.-%, mmf); fluorinite (6-7 vol.-%, mmf); and liptodetrinite (7-8 vol.-%, mmf). GC-MS study recognized aliphatic lipids and terpenoids in chloroform extracts from the Lom lignite. Aliphatic fraction was dominated by des-A-triterpenoids and monoaromatic triterpenoids. Alkanes with odd-numbered prevalence were registered as well. In aromatic fraction triaromatic oleananes, ursanes and lupines were identified. Olean-12- ene, Ursa-dien-3-one and Amyrones were the highest peaks in GC-MS separation. Series of alkenones, maximizing at C29, C31, C33 were also detected. Biomarker assemblage of the aliphatic portion is completely different in composition to other Bulgarian Neogene coals. For example, the Thracian lignites from Maritza-East, Maritza-West and Elhovo basins, are characterized by high amounts of diterpenoids (Phyllocladane dominance), whereas the Chukurovo lignite (Sofia coal-bearing province) is characterized by a high quantity of diterpenoids and subordinate sesquiterpenoids. However, not even traces of those compounds were detected in Lom lignites. The identified triterpenoids and des-A-triterpenoids of the oleanane, ursane and lupane structural classes are characteristic for Angiosperms contribution. The results indicate a high input of Angiosperm-derived aliphatic lipids to the coal-forming swamp. The presence of des-A-triterpenoids suggests that photochemical and/or microbial processes also contributed to the alteration of the organic matter. Alkanones (C23 - C33) should not be neglected as they are a hint for organic matter transformation in aquatic media. The present results should be regarded as preliminary, since they are based on limited number of samples. Nevertheless, the data unequivocally pointed Angiosperms as dominant contributors to the peat formation. Respectively, Lom coal could be regarded as Angiosperm-derived lignite.
17 th Patras 2005: 57 Annual Meeting of the ICCP
ORGANIC PETROLOGY AND MINERALOGY OF COALS FROM MARITZA-WEST BASIN, BULGARIA
Kostova, I.1, Zdravkov, A.2
1 Sofia University “St. Kl. Ohridski”, Department of Geology and Paleontology 2 University of Mining and Geology, Department of Economic Geology ([email protected])
The Maritza-West coal basin is situated in the southern part of central Bulgaria within the range of the Thracian coal province. The coal is of low rank, of Upper Miocene age and is characterized by high ash yields and sulphur contents. It formed in a rheotrophic, low-lying mire with high pH value. The maceral composition is dominated by humodetrinite macerals. Both attrinite and densinite were recognized in considerable amounts, indicating that the peat formed due to deposition of vegetation under low preservation. Nevertheless, small part of the groundmass probably also formed as a result of the process of mechanical destruction prior to the burial. Non-conifer trees and shrubs were most likely the main contributors to peat formation, as indicated by the enhanced gelification of the humotelinite macerals, as well as by the absence of resin impregnated tissues. During peat accumulation small areas with open water formed in which algae thrived. The latter is consistent with the observation that the peat deposited in a wet environment, which resulted in an enhanced gelification of the organic matter. Despite of the wet conditions the thermal destruction took also place throughout the peat deposition. The inorganic matter is represented by silicates, sulphides, sulphates, oxides, hydroxides and carbonates. Calcite, pyrite, gypsum, chlorite and illite are the major minerals in the studied coal. Quartz, montmorillonite, plagioclase, K-feldspar, kaolinite, aragonite, opal, jarosite, hematite and limonite, are present in smaller amount. Gypsum and pyrite are the main sulphur-bearing minerals in these high-sulphur coals.
18 th Patras 2005: 57 Annual Meeting of the ICCP
DIFFERENT TYPES OF ORGANIC MATTER FROM ANADYR BASIN (NORTH-EAST RUSSIA)
Pronina, N.V., Fadeeva, N.P.
Department of Geology, Moscow State University, 119234, Vorobyovy Gory, MSU, Moscow, Russia ([email protected])
In geology, there are many examples of co-existence of coal- and oil/gas-bearing formations in sedimentary basins. Many studies worldwide are devoted to this theme. The objects for such investigations are known in Palaeozoic, Mesozoic and Cenozoic sedimentary formations. This analysis refers to Anadyr basin that is situated in the most N-E part of Russia. It extends from the Anadyr coal basin (which constitutes the continental part being mined since the 1930’s) to the shelf of Beringovo sea (region perspective for oil/gas). The total area of the basin is more than 70,000 km2. The thickness of Cenozoic sedimentary rocks is more than 7-7.5 km. Palaeogene deposits are represented by volcanic-sedimentary rocks; Neogene is composed by terrigenous rocks of continental, coastal and marine genesis. Coal beds in the Anadyr basin are found in Palaeocene-Eocene and in Miocene strata. In the Palaeogene part of the sequence there are many thin coal beds, but only some of them have a mineable thickness. In the Miocene part there is a 45-m thick bed of brown coal. All the coals are humic. Petrographic composition of coals is characterized by the predominance of vitrinite (≥80%) that is represented by gelinite, collotelinite and rare telinite. Liptinite (usually 10-15%, rare – up to 30-35%) is represented by cutinite, resinite, sporinite and suberinite. Inertinite macerals are rare (their amount doesn’t exceed 2-3%) and usually found as small fragments of fusinite in collotelinite. Random reflectance of vitrinite measured in air showed that coals of Neogene age are of brown coal rank (<7.4%) and these from Palaeogene strata are hard coals (7.8-8.0%). Besides coal beds that represent typical humic organic matter, the organic matter (OM) from aquatic part of the basin was examined.
Maynitskaya formation (Pg 1-2) is the main oil-source rock in the Cenozoic sedimentary sequence of the Anadyr basin. Petrographic characteristics of kerogen from Maynitskaya siltstones confirms its oil-source properties, because its OM consists of amorphous yellowish-brown matrix, rich in pyrite that can be considered colloalginite, or mixtinite abound in liptinite macerals. According to Rock-Eval analysis (Tmax up to 435oC and higher) these strata is within “oil window”. The Miocene part of the sequence mainly consists of humic OM (H/C = 0.78-1.15, HI = 50-350 mgHC/gTOC) and has low rank of its transformation. That is why it can be considered a gas-source formation. Comparison of geological structure of Anadyr basin with the coeval basins of Southern Sakhalin (Aniva region) and Australian Latrobe Valley/Gippsland showed that they have very much in common. They have similar age, OM composition and some other lithological and tectonic characteristics. This gives ground to refer all these basins to the united Pacific mobile tectonic province (its western part) and to correlate them to the coal- and oil/gas-bearing formations of American continent (eastern part).
19 th Patras 2005: 57 Annual Meeting of the ICCP
PETROLOGICAL AND GEOCHEMICAL CHARACTERISTICS OF PEAT FROM THE KRÁSNO PEAT BOG, CZECH REPUBLIC
Sýkorová, I.1, Machovič, V.2, Mizera, J.3, Havelcová, M.1, Vašíček, M.1
1 Institute of Rock Structure and Mechanics AS CR, V Holešovičkách 41, 182 09 Prague, Czech Republic ([email protected]) 2 Institute of Chemical Technology Prague, Technická 5, 162 08 Prague, Czech Republic 3 Nuclear Physic Institute AS CR, CZ 250 68 Řež near Prague, Czech Republic
Six peat samples representing a two meters vertical profile in the western part of the Holocene Krásno peat deposit in the Krušné Hory Mountains in western Bohemia, were analyzed for elemental, maceral and mineral composition. The occurrence of functional groups in peat and their humic acids, as well as 40 trace elements were determined. Three main strata were recognized in the profile: i) thick light brown layer of non- decomposed or slightly decomposed Sphagnum plants with remains of higher plants, ii) dark brown mineralized and highly decomposed layer of Sphagnum and Carex plants with woody remains, and iii) grey brown mineralized and highly decomposed peat layer. The sharp transition from highly decomposed to non-decomposed peat is related to the increase of TPI index, C/N and O/C atomic ratio, and the decrease of GI index, ash, carbon and sulfur contents, amounts of carbonyl and carboxyl functional groups, and yields of humic acids. The base of the profile contains from 28 to 65% of ash. Quartz, K-feldspars, biotite, amphiboles are the most abundant in the mineral matter. Kaolinite, carbonates and Fe compounds are very fine dispersed in both mineral and organic phases. Compared to slightly decomposed peat, mineralized peat appeared to be enriched in Cd, Co, Cu, Ge, Ga, Hf, Se, Th, U and Zn. Two main trends in distribution of trace elements in the profile were found. The majority of the elements show a general increase of the trace elements content by increasing ash content, while the elements Au, Br, Hg, La and W show a decrease by the increase of the ash content. The highest concentrations of As, Ba, Cr, Fe, K, Mo, Na, Rb, Sr, Ta were found in the deepest layer of the peat bog profile probably due to the influence of the basal sediments and/or ground water.
Acknowledgements: This study was financed through Grant No. IAA 300460510 by the Grant Agency of the Academy of Sciences of the Czech Republic.
20 th Patras 2005: 57 Annual Meeting of the ICCP
SOME GEOCHEMICAL CHARACTERISTICS OF SOKO BANJA LOW RANK COAL, EASTERN SERBIA
Životić, D.1, Lorenz, H.2, Grzetić, I.3, Ercegovac, M.4, Simić, V.1
1 Faculty of Mining and Geology, University of Belgrade, Djušina 7, 11000 Belgrade, Serbia and Montenegro ([email protected]) 2 Bundesanstalt für Geowissenschaften und Rohstoffe, Stilleweg 2, 30655 Hannover, Germany 3 Faculty of Chemistry, University of Belgrade, Studentski trg 12-16, 11000 Belgrade, Serbia and Montenegro, 4 Serbian Academy of Sciences and Arts, Knez Mihailova 35, 11000 Belgrade, Serbia and Montenegro
Ten coal samples and two carbonaceous clay samples were collected from fresh, working faces in the Soko underground mine, Soko Banja basin, Eastern Serbia. All samples were collected from different parts of the main seam (Čitluk series). The brown coals from Soko Banja basin are of Lower Miocene age and are classified as typical humic coals, telohuminitic-detrohuminitic type with low content of inertinite and liptinite. According to the average huminite reflectance (0.40% Rr), the Soko Banja coal is a sub-bituminous B coal (Mattbraunkohle). Major elements (Al, Ca, Cl, F, Fe, K, Mg, Na, P, S, Si) were analysed using X-Ray Fluorescence (XRF). Trace elements were analysed by Inductively Coupled Plasma- Mass Spectrometry (ICP-MS) and XRF. In comparison with world lignites, using the geometric mean value, coal from Soko Banja basin has high strontium content. Higher values than these of the world lignites were obtained for Mo, Ni, Se, U and W. Correlation analysis shows the inorganic affinity for almost all major and trace elements. Only S reveals organic affinity. The content of some elements such as Ti, V and Zr, considerably varies when analysed by both applied methods on the same sample. These differences are apparently caused by the different amounts of mineral-bituminous groundmass in them. We suppose that not all amounts of these elements were extracted during preparation for ICP-MS, and that in such cases XRF gave more reliable results. The highest variations of results were recorded in samples rich in mineral-bituminous groundmass.
21 th Patras 2005: 57 Annual Meeting of the ICCP
GEOLOGICAL AND PETROGRAPHIC CHARACTERISATION FOR PHOSPHOROUS DISTRIBUTION IN SOME COAL SEAMS OF JHARIA COALFIELD, JHARKHAND, INDIA
Varma, A.K., Mishra, S.
Coal Geology and Organic Petrology Lab., Dept. of Applied Geology, Indian School of Mines, Dhanbad—826004, Jharkhand, India ([email protected])
Phosphorous distribution in inertinite-rich coal seams (Immf > 30 vol.-%) was investigated in Barakar Formation (lower Permian) coal seams of Jharia coalfield. Technological properties, petrographic composition, vitrinite reflectance measurement, scanning electron microscopy (SEM) and phosphorous content determination were carried to investigate nature, occurrence and variation of phosphorous minerals in different coal seams with respect to ash content, coal rank, maceral composition, lithotype, cleats, intrusive effect as well as faulting. The average content of phosphorous was found to vary in range of 0.03 to 0.23 wt.-%. The various phosphorous minerals identified are mainly apatite, goyezite and gorcexite. Scanning electron microscopy (SEM) indicated that phosphorous bearing minerals are associated with inertinitic vesicles. Cleats, which are also filled with minerals, as seen in petrographic studies found to lack phosphorous bearing minerals. It appears that phosphorous content in coal is directly proportional to its inertinite content. Phosphorous content indicates very good positive correlation with the ash content and the dull bands of the coal. It seems that phosphorous was apparently released in a more soluble form and then reprecipitated with other available ions in the pores of peat bed during peat formation. The phosphorous content at mica-lamprophyre intrusion is found to have same background value of the seam, but its concentration increases drastically within a short distance (~10 m) from the intrusion, where natural coke has formed. It can be explained as chemically active fluids migrating from mica-lamprophyre dyke would have encountered clays and organic functionality for the first time in this area. These clays and/or organics might have played important role in precipitation, and accumulation of phosphorous-bearing mineral matter in the natural coke and coal, influenced by intrusions. The fault appears to have no visible impact on phosphorous distribution when it has not been associated with any igneous activities and mineralizing fluids.
22 th Patras 2005: 57 Annual Meeting of the ICCP
PETROLOGY, CHEMISTRY AND STATISTICAL EVALUATION OF MAJOR AND TRACE ELEMENT DISTRIBUTION IN PERMIAN COALS FROM THE PARANÁ BASIN: SANTA TEREZINHA, LEÃO-BUTIÁ AND CANDIOTA COALFIELDS, RIO GRANDE DO SUL, BRAZIL
Kalkreuth, W.1, Willett, J.2, Finkelman, R.2, Burger, H.3, Holz, M.1, Kern, M.1, Machado, G.1, Mexias, A.1, Silva, M.1
1 Instituto de Geociências, UFRGS, Av. Bento Gonçalves, 9500,91501-970 Porto Alegre, RS, Brazil ([email protected]) 2 U.S. Geological Survey, Mail Stop 956, Reston, VA 20192, USA 3 Freie Universität Berlin, Geoinformatik, Malteserstr. 74-100, 12249 Berlin, Germany
The current paper presents results on petrological and geochemical coal seam characterization in Permian coal-bearing strata from the Paraná Basin, southern Brazil. Sequence stratigraphic analysis shows that peat accumulation in Permian time was closely linked to transgressive/regressive cycles, with peat accumulation occurring in a predominantly back barrier/lagoonal setting. Coal petrographic analysis indicates subbituminous coals at Candiota and Leão-Butiá and high volatile bituminous coals at Santa Terezinha, where locally the coal seams are thermally altered by volcanic intrusions. Petrographic composition is highly variable, with seams at Candiota and Santa Terezinha frequently enriched in inertinite. Chemical analyses indicate that all coals are mineral matter-rich (mean 49.09 wt.-%), with SiO2 and Al2O3 dominating as determined by ICP-AES. Quartz is also the predominant mineral detected by X-ray diffraction, where it is associated with feldspar, kaolinite and hematite and iron-rich carbonates. The results from Scanning Electron Microscopy are broadly consistent with the bulk chemical and mineralogical analyses. Quartz and clays are common in all samples analyzed. Other minerals observed were amongst others carbonates, pyrite, calcite, monazite, kaolinite, barite, sphalerite, rutile and quartz of volcanic origin. The distribution of trace elements is well within the range typical for coal basins of other areas despite the fact that the Paraná Basin coals are very high in ash yields. The average concentrations for elements of environmental concern (As, B, Be, Cd, Co, Cr, Cu, Hg, Li, Mn, Mo, Ni, Pb, Sb, Se, Tl, U, V, Zn) are similar to or less than the mean values for U.S. coal. However, considered on an equal energy basis, Paraná Basin coals will produce in combustion 5 to 10 times the amount of most elements compared to an equal weight US coal. Hierarchical cluster analysis identified three groups of major minerals and eleven groups of trace elements based on similarity levels. On a regional scale the coalfields can be separated by the differences in rank (Candiota and Leão-Butiá versus Santa Terezinha) and by applying discriminant analysis based on 4 trace elements (Li, As, Sr, Sb). Highest Rb and Sr values occur at Candiota and are linked to syngenetic volcanism of the area, whereas high Y and Sr values at Santa Terezinha can be related to the frequent diabase intrusions in that area.
23 th Patras 2005: 57 Annual Meeting of the ICCP
PETROGRAHY AND ISOTOPE GEOCHEMISTRY OF HUNGARIAN POWER SUPPLY COALS
Hámor-Vidó, M.1, Hámor, T.2
1 Geological Institute of Hungary, H-1143 Budapest, Stefánia st. 14, Hungary ([email protected]) 2 Hungarian Geological Survey, H-1143 Budapest, Stefánia st. 14, Hungary
The present work is a major step in establishing the stable isotopic database of the Pannonian Basin coals. Organic petrographic maceral composition, proximate analysis 34 34 13 and determination of δ Sorg, δ Spyrite and bulk δ C ratios of coals used for power generation in Hungary were carried out following a representative sampling campaign. The out coming database will support assessing the potential future use of coals in power generation by considering their environmental risks, especially the characterization of the formation of the different sulphur phases. The maceral composition, sulphur content and C, S isotopic signatures and some of the geological evidences published earlier show that the majority of these coals were deposited in a freshwater environment, in spite of the relatively high average sulphur content. However, many of the studied Upper Cretaceous, Lower Jurassic, Eocene and Lower Miocene formations have coals of marine origin as indicated by their maceral composition and sulphur and carbon chemistry. Carbon isotope values vary within a range of -23.92‰ and -28.54‰. The mean values of the different ages fit well to the global average for terrestrial OM but the range is somewhat higher than the relevant data in the literature. Preservation of OM played an important role in the carbon isotopic ratio changes. The lighter isotopic compositions and the higher TPI indices represent an environment with restricted access to oxygen. The major part of sulphur content is associated with the organic matter. All studied 34 34 34 sulphur phases are relatively enriched in δ S isotopes (δ Sorg 13.03‰; and δ Spyrite 10.33‰ in average), which indicate that marine bacterial sulphate reduction had a minor role in their formation and/or the interstitial spaces were closed rapidly in the peat during the early diagenesis leading to an enforced relative enrichment of the heavy sulphur isotopes.
24 th Patras 2005: 57 Annual Meeting of the ICCP
CAN MERCURY BE REDUCED IN FEED COAL AND STACK EMISSION? ROLE OF ORGANIC MATTER - A CANADIAN EXAMPLE
Goodarzi, F.
Environmental Study Group, Geological Survey of Canada – Calgary, 3303-33rd Street N.W., Calgary, Alberta, Canada, T2L 2A7 ([email protected])
Western Canadian sub-bituminous coal is mined using strip-mining methods. The coal is used to feed coal-fired power plants to generate electricity. There are parameters that influence the mercury content of these coals, such as the occurrence and frequency of parting in the seam, weathering and epigenetic mineralization. Selective mining and removing the layer of coal containing higher amounts of mercury can result in the reduction of mercury in feed coal. By removing partings and coal layers containing high amounts of mercury through selective mining, the mercury content in “as-mined” coal can be reduced by as much as 60%. Six power plants burning pulverized subbituminous coal in western Canada were sampled using the Ontario Hydro method and mercury in the coal was determined using CVAAS. It was found that the gaseous elemental mercury (GEM, Hg0) is emitted at a rate of 6.6 to 12.6 g/hr. The mass balances for the six power plants are between 86% and 123% and were calculated from the results of three tests performed at each power plant. Variability in the mass balances may be related to the difference in the coal feed rate. The mercury and maceral content of the six feed coals burned were measured and compared to the mercury and carbon content of corresponding fly ashes. The fly ashes were collected from electrostatic precipitator (ESP) pollution controls used at the power plants. Four feed coals from the Scollard Formation, Upper Cretaceous to Tertiary in age were deposited in a freshwater depositional environment and contain 35 to 44% inertinite. Two feed coals from the Horseshow Canyon Formation, Upper Cretaceous in age, were deposited in a brackish water environment and contain 14% inertinite. The inertinite content of feed coals was related to their depositional environments, such that it was greater for coal deposited under fresh water conditions (35 to 44%) compared to coal deposited under brackish water conditions (14%). The data indicates that the inertinite content of a coal seam may be indicative of the percentage of unburned carbon, and the percentage of mercury captured by a cold-side ESP.
25 th Patras 2005: 57 Annual Meeting of the ICCP
COMPOSITIONAL DIFFERENCES IN DIAGENETIC CARBONATES FROM COAL-BEARING DEPOSITS OF THE PECHORA BASIN, RUSSIA
Rasulov, A.
Institute Geology and Geochemistry, Uralian Branch, Russian Academy of Sciences, Pochtovy per. 7, Ekaterinburg, 620151 Russia
The studied basin is located in the north-western margin of Europe. The Permian section, ranging in thickness from 0.2 to approximately 5.5 km, is divided into the Yunyaginskaya, Vorkutskaya and Pechorskaya formations. The Vorkutskaya formation is a main coal-bearing unit, which includes fine-grained terrigenous rocks ranging from Kungurian to Ufumian in age. This formation consists of alternating sandstones, siltstones, shales and coal seams that accumulated in flood plain, barrier bar, lagoon, and swamped-lake environments. Diagenetic carbonates were studied in Inta, Vorkuta, Siryaga and Chalmeryu coal fields. They occur mainly in organic rich claystones, siltstones, and usually form thin beds or elongated concretions with their long axes coinciding to the host rocks lamination. According to results of chemical, thermal, X-ray and UR spectroscopy analyses the investigated carbonates include one or two carbonate minerals and some times three: calcite, dolomite and siderite. In all the coal fields of the Pechora basin, monomineralic concretions predominate consisting of siderite. In respect to composition, mixed concretions in the Vorkuta, Siryaga and Chalmeryu areas include siderite and dolomite. But in the south of the basin (Inta district), concretions contain calcite and siderite. We consider that precipitation of diagenetic carbonates is a process, in which microbial metabolic activities play an important role. In subsurface sediments, around the sites of dead organisms, a bacterial population starts building up a colony using as food, among other things, metal-organic compounds containing Ca, Mg, and Fe ions. Decomposition of the acids by micro heterotrophs leads to release of organic-bound metallic ions producing extra- or intracellularely inorganic compounds. According to this scenario, mineral composition of diagenetic carbonates is largely related both to the types of metal-organic compounds present in the bottom waters and the nature of associated bacterial community. From this point of view deposition of coal-bearing formation in the north and south of the Pechora basin took place under different biological activity and landscape biogeochemistry.
26 th Patras 2005: 57 Annual Meeting of the ICCP
TRACING ANTHROPOGENIC IMPACTS IN ASSOCIATION WITH ENVIRONMENTAL CHANGES IN LAKE BALATON SEDIMENTS USING ORGANIC PETROLOGY
Hámor-Vidó, M., Cserny, T., Kuti, L.
Geological Institute of Hungary, Stefánia st. 14, H-1143 Budapest, Hungary ([email protected])
Lake Balaton is a Post Glacial-Holocene lake located along and associated with SW-NE tectonic strikes in the centre of the Pannonian Basin. A sedimentary profile of the Lake Balaton was studied in borehole Ba-10/98.2, in the Keszthely Bay in the vicinity of the inflow area of Zala River. Twelve core samples taken from the borehole were studied by means of organic petrology, moisture content, density and carbonate content determination to describe sedimentary changes in the profile. The profile is divided into four horizons, named “A”, ”B”, “C”, “D” on the basis of the macroscopic features, where the uppermost zone is “A” and the lowermost is “D”. The 0.6-m thick Holocene sequence represents a period of ca. 100 years. The depositional environment at the bottom layers indicate limnic conditions with low organic matter content (“D”), that was followed by a mixed limnic and fluvial sedimentation (“C”-“B”) controlled by the introduction of a new drainage system of the Zala River in the west. In the uppermost layers (“A”), well-aerated limnic sedimentation is detected due to the man-made restoration of the Little Balaton area, which protects the Keszthely Bay from the high sedimentary input of the Zala River. The sediments of horizons “A”, “B”, “C” are unconsolidated calcareous mud, and slightly consolidated carbonaceous silty mud at the bottom (“D”). They are usually rich in organic matter. The most characteristic maceral in the whole profile is huminite, which varies between 28% and 60% and often shows transition to “cutinite-like maceral” in the upper samples up to a depth of 0.3 m beneath surface due to a very low grade diagenesis. This type of tissue usually contains cellulose (visible under UV excitation) and its optical property is very similar to liptinite. In the lowest horizon “D” below 0.45 m (limnic conditions), alginite, sporinite and textinite are the dominant macerals. Among sporinite, conifer pollens are very frequent and especially in the lowermost sample the sporinite content reaches 20.2% of the total OM. In the horizon “C” gelified or partly gelified huminite particles of 0.002-0.015 mm in diameter and the occurrence of humodetrinite with oxidized particles indicate transportation of the organic material. In the upper part of the horizon “C”, 21.11% pyrofusinite shows an extended fire in the land. Eutrophism of the lake in the period of mixed sedimentation in horizon “C”-“B” (between 0.45-0.075 m) is detected by continuous increase of alginite, sporinite, liptodetrinite and humodetrinite contents in the OM. In this zone the early diagenetic oxic conditions and the sediment reworking are confirmed by the presence of weathered equant pyrite minerals and macrinite as well. Subsequent to the restoration of Little Balaton, above 0.075 m depth, in horizon “A” the amount of OM has decreased and the detritus material of huminite and liptinite has minor importance in the maceral composition.
27 th Patras 2005: 57 Annual Meeting of the ICCP
THERMAL ALTERATION OF COALS IN THE KHASYN COALFIELD (MAGADAN REGION, RUSSIA)
Stukalova, I.E.1, Rusinova, O.V.2
1 Geological Institute of the Russian Academy of Sciences, Pyzhevskyi per. 7, Moscow, 119017 Russia ([email protected]) 2 Central Research Institute of Geological Prospecting for Base and Precious Metals, Moscow, Russia
The aim of the investigation was to understand the nature and specific structural properties of organic matter (both concentrated and dispersed in rock) produced by thermally altered coals of the Khasyn coalfield. What is actually happening to the coal and rock matter when they contact directly in the course of the cooling intrusion? We tried to answer it by studying series of samples of almost unchanged coal, the coal fragments within a diabase dyke and the proper diabase dyke rocks enriched by fine- dispersed organic matter. The problem was to show how the structure and characteristics of coal matter changed during its contact with a diabase dyke, and what products of its transformation enriched the dyke’s matter. The Khasyn coalfield is located in the Magadan region in Russia, 82 km north of the town of Magadan. There are 12 coal occurrences and two coal basins in the Magadan region. The region is peculiar for high ash content in the coal and the ‘intrusive bodies - coal beds’ contacts. The Khasyn coalfield is structurally associated with the Okhotsk- Chukotka volcanic belt. Lower Cretaceous coal deposits are believed to occur in the area of recurrent Cretaceous to Palaeogene volcanic and intrusive activity. Coal-bearing Lower Cretaceous Khasyn formation (255 to 455 m thick) consists of sandstones, tuffstones, mudstones, siltstones and coal seams with variable thickness ranging from 0.6 to 5 meters (1.40-2.40 m on average). Methods of coal petrography and X-ray analyses were used for detailed examination of coals, dispersed organic matter and rocks.The rank of coals developed in the Khasyn coalfield is typically similar to the grades of low volatile bituminous and semi- anthracites (Ro = 1.70-2.10%). The samples obtained at the direct contact of the diabase dyke present coal fragments, which had suffered some thermal influence manifested in high coal rank with metallic lustre and high anisotrophy, typical of anthracite of high degree of metamorphism, with reflectance value (Ro = 4.41-5.50%). The matter located at the direct contact with the dyke demonstrates two distinctly manifested types of coaly matter with properties typical of transitional stages from anthracites to graphites: high anisotropic properties, changed internal structure, high reflectance value.
The X-ray characteristics (d002 and Lc) were obtained for samples of the three above series, i.e., for coal, coal inclusions in the diabase dyke and dispersed carbonaceous matter in the dyke rocks. The coal samples (d002 = 3.45 Å, Lc = 37 Å) occur in the diagram d002-Lc in the area of coaly material. Coaly inclusions in the dyke (d002 = 3.43 Å, Lc=24 Å) occur in the area of disordered graphite. Dispersed carbonaceous matter in the dyke rocks (d002 = 3.43 Å, Lc = 21 Å) occurs near the area of coaly material- disordered graphite.
28 th Patras 2005: 57 Annual Meeting of the ICCP
INTERNAL STRUCTURE OF THERMALLY ALTERED VITRINITE IN THE VIEW OF FTIR AND RAMAN SPECTROSCOPY EXAMINATION
Morga, R., Komorek, J.
Institute of Applied Geology, Silesian University of Technology, Gliwice, Poland ([email protected])
From three channel samples of coal (steam coal Rr = 0.71%, coking coal Rr = 1.17% and anthracite Rr = 2.86%), collected from seams of the Upper Silesian Coal Basin, vitrinite concentrates were obtained. They contained from 90 to 98% of vitrinite. The concentrates were heated at temperatures of 400, 600, 800 and 1200oC, for one hour, in an argon atmosphere. Heating at lower temperatures results in gradual aromatisation of vitrinite in all the three o concentrates (increase of Aar/Aal ratio). This process takes place from 400 C (coking coal and anthracite) and up to 600oC (steam coal). With progressive heating most of the o absorption bands decrease. At 1200 C, νC=Car+νC=O, δCH3+δCH2 and δCHar bands can still be seen in the FTIR spectra. High background indicates high degree of condensation of aromatic compounds or can result from scattering of radiation on coal particles. Beginning from 400oC, the increase of the 1600 cm-1 band intensity in the Raman spectra of vitrinite from the steam coal, suggests slight changes towards graphitization. At 600oC the 1350 cm-1 band also increases; this shows intensification of structural defects. For vitrinite from the coking coal, the intensity of the 1600 cm-1 band increases faster indicating stronger graphitization. Beginning from 800oC, however, the rate of this process becomes slower. With progressive heating the intensity of the 1350 cm-1 band also increases. This reflects the occurrence of disturbances in the internal structure of vitrinite. Raman spectra obtained from anthracite show that graphitization starts not earlier than after heating at 800oC. It is accompanied by intensification of structural defects, which can be caused by growth of the crystallites.
29 th Patras 2005: 57 Annual Meeting of the ICCP
OPTICAL PROPERTIES OF SPORINITE AND SEMIFUSINITE SUBJECTED TO THERMAL TREATMENT
Komorek, J., Morga R.
Institute of Applied Geology, Silesian University of Technology, Gliwice, Poland ([email protected])
Examination was performed on liptinite and inertinite concentrates prepared from channel samples of steam coal (Rr = 0.70%) and coking coal (Rr = 1.25%), collected from seam 405 of the Upper Silesian Coal Basin. The concentrates were heated at temperatures of 400, 500, 600, 800, 1000 and 1200oC, for one hour, in an argon atmosphere. After heating, the samples were subjected to reflectance measurements. Employing the method of W.E. Kilby, the true maximum (Rmax), intermediate (Rint) and minimum (Rmin) reflectances of sporinite, semifusinite and liptinite coke matrix were evaluated. Their reflectance anisotropy and RIS shapes were also determined. After heating at 1200oC sporinite in the two samples has similar reflectance and degree of optical anisotropy. Random reflectance value (Rr) for steam coal concentrate is 8.01% (sr = 0.38%), while for coking coal concentrate 7.42% (sr = 0.45%). The true maximum and minimum reflectance values are 8.55% and 6.81%, as well as 8.64% and 6.27%, respectively. Bireflectance (Rbi) reaches 1.74% and 2.37%, respectively. RIS shape is biaxial negative or biaxial positive-negative. Matrix of liptinite coke formed from the steam coal has lower random reflectance value and lower anisotropy than in the coke from the coking coal. RIS shape is the same – biaxial negative. At 1200oC random reflectance of semifusinite from the steam coal is 10.42%. The true maximum and minimum reflectance values are 12.32% and 7.60%. Bireflectance reaches the value of 4.72%. Random reflectance of semifusinite from the coking coal is 9.97%. The true reflectance values are 11.58% and 8.04%, respectively. Bireflectance value equals 3.54%. RIS shape in both cases is biaxial negative.
30 th Patras 2005: 57 Annual Meeting of the ICCP
ORGANIC PETROLOGY OF RECENT LACUSTRINE SEDIMENTS DURING THERMAL ALTERATION BY ROCK-EVAL PYROLYSIS
Sanei, H., Stasiuk, L.D., Goodarzi, F.
Geological Survey of Canada, Calgary 3303-33rd Street, N.W. Calgary, AB, Canada T2L 2A7 ([email protected])
This study characterizes the petrological changes occurring in an organic matter assemblage of recent lacustrine sediments from Alberta, Canada, during the various steps of Rock-Eval 6® pyrolysis. The experimental procedure was designed to study the organic petrology of the bulk sediment samples, (i) before thermal alteration by Rock- Eval pyrolysis; (ii) after pyrolysis of the sediments between 100ºC to 300°C (at rate of 25ºC/min) using Rock-Eval 6®, where the S1 peak was evolved and the “volatiles” free hydrocarbons were released from the samples; (iii) after pyrolysis of the sediments up to 650°C in Rock-Eval 6 pyrolysis oven, where a bimodal S2 peak was fully evolved and hydrocarbons were released from the sample; (iv) after the complete thermal degradation of organic matter where samples were heated in a pyrolysis oven, and then in an oxidation oven to a temperature of up to 850°C. The results indicate that the organic compounds released during pyrolysis at low temperatures of up to 300°C (mainly S1-compounds) are most likely derived from a ‘stain-like’ amorphous organic matter (AOM), including pigments and oils/lipid products with strong, multicolored VIS fluorescence. The fluid characteristics of the thermally labile S1-compounds possibly account for the significant grain surface coating by the organic matter. Thermal alteration of sediments at 300°C results in the transformation of some alginite and other macerals into a secondary product of blue fluorescing bitumen, which migrates into available free spaces. The release of S2-compounds during high temperature pyrolysis (from 300 to 650°C) causes severe alterations in the morphology of the liptinitic organic matter and the formation of pyrobitumen. A bright yellow fluorescence that appeared at this stage is likely due to thermal transformation of bitumen produced in S1 pyrolysis and other liptinitic macerals into an “oily-material”, which fills cell lumens and becomes incorporated into the mineral matter. The rapid rate of heating (25°C /min) and sample residence time during Rock-Eval pyrolysis are insufficient for complete thermal destruction of the secondary liquefied hydrocarbons in the sample.
31 th Patras 2005: 57 Annual Meeting of the ICCP
PETROGRAPHIC AND CHROMATOGRAPHIC INVESTIGATIONS ON ORGANIC COMPONENTS IN THERMALLY ALTERED COAL WASTE
Misz, M., Fabiańska, M., Ćmiel, S.
University of Silesia, Faculty of Earth Sciences, ul. Będzińska 60, 41–200 Poland ([email protected])
The waste produced by coal exploitation in Upper Silesia (Poland) is stored in 136 coal waste dumps. Some of these dumps are characterized by elevated temperatures that result in various environmental and ecological problems. The aim of the work reported here is to establish the degree of geochemical and petrographic change occurring in organic matter in these waste dumps. Samples of coal waste were collected at various distances (from 0.05 to > 4 m) from a subsurface fire in a waste dump at Piekary Śląskie (Upper Silesia, Poland). Maceral and reflectance analyses of the samples were carried out using an Axioplan II optical microscope. GC-MS analyses involved a gas chromatograph equipped with a DB-35 column (60m x 0.25mm x 0.25µm) coupled to a mass spectrometer (EI at 70 eV, full scan, 50-650 da). All compounds were identified by their mass spectra, their retention times and by reference to literature data. All three maceral groups, coke and mineral matter occur in the analysed samples. The most abundant group of macerals is vitrinite (6–63%). These macerals are typically altered by weathering and/or heat. The transformations are demonstrated by oxidation rims, pores and by rims surrounding trimacerite particles. Some samples contain both altered and unaltered vitrinite particles. Inertinite, present in all samples, varies in quantity from 1–26%. Liptinite contents range up to 17%. Some liptinite particles show cracks and pores. Hydrocarbon droplets may reflect elevated temperatures. Some samples contain up to 92% coke as particles that are massive and porous. The vitrinite reflectance of the examined material ranges from 0.62-6.27%. GC-MS analyses show that coal extracts display features that are typical for low- temperature coal tars. The aliphatic hydrocarbon compounds are dominated by n- alkanes together with n-alkenes with distributions that follow the n-alkane envelope. A wide range of polycyclic aromatic hydrocarbons with 2-5 rings was identified together with their aliphatic derivatives. To assess the extent of heat-induced thermal changes in organic matter, several thermal maturity biomarker parameters based on aliphatic and aromatic hydrocarbons were calculated. The range of the calculated values is wide. They vary from values that indicate, in samples that are relatively thermally unaltered, the beginning of catagenesis up to values, in mature samples, that correspond to the beginning of metagenesis. The microscopic and GC-MS analyses suggest an increase in the thermal transformation of organic matter as a known heat source is approached and a comparable decrease in the effects of weathering. Such analyses may be of value in defining the impact of the coal waste dumps on their surroundings and contribute to the managing of coal waste with elevated temperatures.
32 th Patras 2005: 57 Annual Meeting of the ICCP
PYROLYTIC BEHAVIOR OF SOME THRACIAN LIGNITE LITHOTYPES, BULGARIA
Stefanova, M.
Institute of Organic Chemistry, Bulgarian Academy of Sciences, Acad. G. Bonchev Str., Block 9, 1113 Sofia, Bulgaria ([email protected])
Analytical pyrolysis coupled with gas chromatography-mass spectrometry (Py-GC/MS) is a powerful technique for structural study of natural biopolymers and geomolecules. The polymeric material undergoes heat-induced bond cleavage and produces lower molecular mass molecules reflecting the composition of the sample under study. The technique is well described with its adventures, drawbacks and the development could be followed in the specialized issues. Recently, the conventional pyrolysis (Curie-point pyrolysis at 510ºC) was improved by flash heating of the sample in the presence of alkylation agents. In our study we shall use both techniques and shall compare the results obtained. The procedure with methylation has advantages over the conventional pyrolysis because it avoids decarboxylation and produces esters and ethers as end products. A broad range of fossils and industrial materials has been studied by pyrolytic technique. Another advantage of pyrolysis is that it could be run in a preparative mode with inner standards and quantitative interpretation of the results. Pyrolysis was applied to a great variety of bio- and geological materials. The technique enabled to distinguish the methoxy groups present in the initial sample (lignin residue in geopolymers) and those produced during analysis. It is a powerful tool for investigation of a set of biopolymers, fossils, i.e. peatified woods, lignins, humic substances, coals, asphaltenes, kerogen of petroleum source rocks, oil shales, etc. There are comparative studies employing pyrolysis among peat and coals of different rank. In our study the attention will be concentrated on lignite, a geological material biogeologically related to lignin. In our previous study we succeeded to obtain, identify and quantify residues of lignin incorporated in coal organic matter. Our results proved the presence of appreciable quantities of preserved lignin moieties in low rank coals. Lignite lithotypes from “Maritza-East” lignite deposit (Bulgaria), i.e. humovitrain, xylain, liptain and humoclarain were under consideration. GC-MS instrument was “on- line” connected to a pyrolytic unit and the vaporized species were analyzed. The main products were lignin-derived phenol derivatives with strong guaiacyl structure dominance (Gymnospermae contribution). There were typical products of coal pyrolysis as well, i.e. alkanes/alkenes, benzenes, phenols, naphthalenes, thiophene, etc., some of them being alkylated. Pyrolytic data confirmed some previously registered features of lithotypes, namely high contribution of Gymnosperms to coal-forming community and total lack of syringic units (Angiosperms). The modest participation of Gramineae in lithotypes organic matter was demonstrated by the low content of coumaryl structures. Py-GC/MS data enrich our knowledge on the chemistry of coal maturation made on the basis of biomarker assembly and residues of lignins.
33 th Patras 2005: 57 Annual Meeting of the ICCP
CHANGES IN THE QUALITY OF COAL - FROM IN-SITU COAL, THROUGH PROCESSING, TO COMMERCIAL COAL
Probierz, K., Marcisz, M.
Institute of Applied Geology, Faculty of Mining and Geology, Silesian University of Technology, Akademicka 2, 44–100 Gliwice, Poland ([email protected])
The changes in the quality of coal from two seams (403/1 and 406/3) located in the western part of Upper Silesian Coal Basin were investigated. The Carboniferous coal seams from Westphalian C are characterized by the occurrence of orthobituminous C, medium grade coals and high maceral contents from vitrinite group. The vitrinite reflectance in the examined parts of the two seams varies within the range of Rr = 0.91- 0.93%. The ash content varies within the range of Ad = 18.0-29.5% (403/1) and 6.4- 9.4% (406/3). The petrographical composition of the studied seams, the technical parameters and their coking properties are also variable. The studied seams show mean thickness 3.0 m (403/1) and 1.9 m (406/3). Precision of evaluation of coal quality parameters was compared on all stages of recognition of the deposit, beginning from prospection, exploration through general exploration to detailed exploration. Coal quality was monitored in the run-of-mine material from the above mentioned seams, worked with the longwall method. The output constitutes a coal blend, which is directed as feed to the preparation plant, where altogether it is simultaneously dressed. The proportion of the coal from seam 403/1 in the total output in relation to the coal from seam 406/3 is 3:2. The changes in coal quality were also examined in the course of coal treatment process, which produces three types of commercial coal on three production lines: commercial coal I – size grade of 20-200 mm, the coal concentrate is extracted in dense-media dressing; commercial coal II – size grade of 2-20 mm, the coal concentrate is extracted in dressing in small coal jigs; commercial coal III – size grade of 0-20 mm, the coal concentrate is extracted in several treatment processes, depending on the grain size, including dressing in small coal jigs, cyclones and floatation. The coal quality parameters are variable in the course of coal production. The ash content (Ad), mineral matter content (MM) and carbominerite and rock content (Cmt) show significant reduction (which proves the effectiveness of the applied treatment processes) accompanied by an increase of the vitrinite content and relatively constant (<10%) liptinite content. The microlithotype, which has the highest content in the studied coal blend, is vitrite, accompanied by trimacerite, vitrinertite and clarite. The content of other microlithotypes is of secondary importance. The treatment processes, despite significant reduction of Ad, MM and Cmt, have hardly any impact on the reduction of sulphur. Other coal quality parameters demonstrate irregular changes, the causes of which cannot always be explicitly explained (for example: variations in coking properties and gross calorific value). Detailed explanation of the reasons for the indicated changes in coal quality parameters in the course of monitoring from in-situ to commercial coal needs further research and more thorough sampling.
34 th Patras 2005: 57 Annual Meeting of the ICCP
SLAG AND FLY ASH DERIVING FROM THE COMBUSTION OF LIGNITE IN PF BOILERS AT THE BEŁCHATÓW POWER STATION (POLAND)
Misz, M.1, Sýkorová, I.2, Machovič, V.2
1 University of Silesia, Faculty of Earth Sciences, Ul. Bedzinska 60, 41-200 Sosnowiec, Poland ([email protected]) 2 Institute of Rock Structure and Mechanics AS CR, V Holešovičkách 41, 182 09 Prague, Czech Republic
Lignite combustion studies tend to focus on the economical and ecological storage and use of fly ash. The redistribution during combustion of elements of ecological significance was the aim of the current project. Some results of a comparative study of the elemental and mineralogical composition of brown coal from Bełchatów mine, Poland, and of the slag and fly ash at Bełchatów Power Station are presented. Representative samples of coal, slag and fly ash were characterized by proximate and ultimate analyses, elemental analyses, micro-FTIR spectrometry, Raman spectrometry, SEM and optical microscopy. The feed coal is a soft brown coal with 65-75% huminite, 5-10% liptinite, < 5% inertinite and 20-30% mineral matter. Clay minerals, particularly kaolinite, are finely and richly dispersed in the detrital organic matter. Quartz is less abundant and calcite is rare as are Ca-, Na- and K-feldspars. Framboids and crystals of pyrite reflect the sulphur content. Contents of As, Cu, and Cr are low. The slag and fly ash comprise original- and newly formed inorganic and organic components. Various elemental- and mineral-concentration trends characterise both combustion products. Slag particles mainly contain quartz, subordinate anhydrite, hematite, and amorphous glassy material and metakaolinite. The latter two are both characterised by variable contents of Si, Al, Ca, Fe, Mg, Ti and S. Slag is relatively enriched in Si, quartz, kaolinite-metakaolinite aggregates, glass and derivatives from coal carbonates (calcite) and pyrite as are chars compared to fly ash. Fly ash contains massive particles of quartz, glassy material and porous dehydrated aluminosilicate particles containing inclusions rich in Ca, Fe, Mg, Ti, Ni, Cr, and V. Compared to slag, fly ash is relatively enriched in Al, Ca, Fe, Mg, Ti, As, Ba, Br, Cd, Cr, Cu, Hf, Ni, Pb, Sb, Zn and Zr. The fly ash is rich in components that originated mainly from clay minerals and feldspars in the original coal. It is also characterized by relatively low proportions of microspheres (enriched in Ca, Si, Al, Fe), resistant quartz, kaolinite- metakaolinite, Ca sulfates, lime, and hematite-magnetite. Unburnt carbon ranges from 1.0-8.1% in slag and from 1.5-6.6% in fly ash. Porous char particles with network textures, and massive particles with light reflectance ranging from 1.5-7.0% Rmax, predominate in char material. Un-reacted huminite and inertinite particles are few. Elemental distribution in slag and fly ash is influenced by initial occurrence, grain size and mineral distribution in the feed coal and combustion conditions. Significant trace element interaction and exchange with ash-forming components occur. An understanding of trace-element- and mineral behaviour during lignite combustion can aid desirable monitoring in thermoelectric power plants and in their environs.
35 th Patras 2005: 57 Annual Meeting of the ICCP
COAL COMBUSTION UNDER OXY-FUEL CONDITIONS. COMPARISON OF THE PETROGRAPHIC CHARACTERISTICS
OF COAL CHARS OBTAINED UNDER O2/N2 AND O2/CO2 ATMOSPHERES
Alvarez, D., Fernández Dominguez, I., Borrego, A.G.
Instituto Nacional del Carbón, CSIC. Apartado 73, 33080 Oviedo, Spain ([email protected])
The increasing concern for CO2 emissions from coal combustion is leading to the investigation of various routes to facilitate the CO2 capture and further sequestration. One of the ways to approach the problem is the combustion of coal in a nitrogen-free atmosphere, which facilitates the step of CO2 separation. In this study two coals of different rank (high and a low volatile bituminous) have been combusted in a drop tube reactor using as reacting atmospheres variable amounts of oxygen (0-21%) in both nitrogen (combustion chars) and CO2 (oxy-chars). Coal particles ground and sieved to 36-75 µm have been pyrolysed/combusted in a drop tube reactor operated at 1300ºC. Special attention has been paid to the influence of oxygen content in the devolatilisation behaviour of coal particles as a function of coal rank. Results show a rather different response of the two coals to the oxygen content in the series O2/N2. The low volatile bituminous coal regularly increased its burnout as the oxygen content in the reacting gas was increased. The spherical and single chambered particles dominating the pyrolysis char changed to highly vesiculated multi-chambered particles as the O2/N2 ratio increased. The CO2 char showed irregular external surfaces and more vesiculated walls than the pyrolysis char and no systematic effect in the morphology of the particles was observed in the oxy-chars as a function of the oxygen amount. Combustion appears to proceed through the structural planes of the anisotropic domains. The behaviour of the high volatile bituminous coal was rather different. The pyrolysis char achieved a very high conversion indicating an enhanced devolatilisation compared to the proximate volatile content of the coal. Low to moderate oxygen contents in the reacting gas (O2/N2<0.1) had a negative effect on the conversion, whereas further oxygen enrichment favoured the burnout. The morphology of the chars obtained under different O2/N2 ratios was rather similar, the main difference being the amount and size of large voids in the walls which appear to be the vehicles through which combustion proceed. The chars obtained under CO2 showed more irregular external surfaces and more vesiculated walls than its N2 counterparts. The conversions achieved by the oxy-chars were systematically lower than those of the combustion chars for equivalent oxygen concentrations. The reflectance of char walls indicated that the chars achieved a lower peak temperature in the oxy-char series.
36 th Patras 2005: 57 Annual Meeting of the ICCP
MICROPETROGRAPHIC CHARACTERISTICS OF THE CHAR TYPES FROM LOW RANK COAL COMBUSTION OF SERBIA
Stojiljković, D.1, Ercegovac, M.2, Radovanović, M.1
1 Faculty of Mechanical Engineering, 27. Marta 80, University of Belgrade, 11000 Belgrade, Serbia and Montenegro 2 Serbian Academy of Sciences and Arts, Knez Mihailova 35, 11000 Belgrade, Serbia and Montenegro ([email protected])
The low rank coals (soft brown coals) of the mines Kolubara and Kosovo are the main energy source in Serbia and Montenegro and the pulverized coal combustion is the dominant technology in power plants. Power plants are the biggest coal consumers, as well as the source of pollutant emissions (SOx, NOx). The release of nitrogen oxides during coal combustion is of major environmental concern. The detailed analysis shows that 35% of the total NOx emission in Serbia is from power plants, as a result of low rank coal combustion. The soft brown coals from Kolubara and Kosovo are of Upper Miocene (Pontian) age and are classified as humic coals of telohuminitic-detrohuminitic type with very low proportion of inertinite and high proportion of xylite (35-40 wt.-%). According to huminite reflectance (0.24-0.30% Rr) and volatile contents (58-62%, daf), they belong to the category of soft brown coals (Low Rank C) with high ash contents (30-43%, dry basis). A drop tube furnace (DTF) was used to simulate the pulverized coal combustion. During the investigations two temperature levels (850 and 950oC) and three coals size fractions (53-63, 90-106 and 180-212 µm) were used. The flue gas was analyzed and the solid residues were collected from the bottom of the furnace and characterized using proximate, ultimate and microscopic analyses. The microscopic investigations of the solid residue provided the quantitative and qualitative analyses of the combustion process, especially in the domain of NO formation and reduction. The morphology of solid residues was studied using samples prepared for the reflected light observation and 12 categories of grains were determined: unchanged and changed coal (homogenous particles and particles with vacuoles), mesosphere, cenosphere (tenuisphere and crassisphere), network (solid and dense char with pores), mixed grains (mixed porous and mixed dense), fusinoid grains, fragments, pyrite and clay. The reflectivity of different grains was found to increase as a function of reaction temperature during the combustion. The knowledge of coal characteristics during combustion can result in improved combustion efficiency and decreased pollutant emissions. The results of DTF investigations have shown the influence of the particle size and temperature on NO formation. NO concentrations decrease with an increase of the temperature and the particle size.
37 th Patras 2005: 57 Annual Meeting of the ICCP
MICROPETROGRAPHIC CHARACTERISTICS OF SOLID RESIDUES AFTER CATALYTIC HYDROGENATION OF THE SERBIAN LOW RANK COALS
Ercegovac, M.1, Aleksic, B.R.2, Cvetkovic, O.G.3, Aleksic, B.D.2, Zivotic, D.4, Vitorovic, D.3
1 Serbian Academy of Sciences and Arts, Knez Mihailova 35,11000 Belgrade, Serbia and Montenegro ([email protected]) 2 IChTM, Center of Catalysis, Njegoševa 12, 11000 Belgrade, Serbia and Montenegro 3 IChTM, Center of Chemistry, Studentski trg 16, 11000 Belgrade, Serbia and Montenegro 4 Faculty of Mining and Geology, University of Belgrade, Djušina 7, 11000 Belgrade, Serbia and Montenegro
Investigating the possibilities of increasing the efficiency of utilization of low rank coals a study of coal conversion into liquid products by direct catalytic hydrogenation has been undertaken. The soft brown coals from Kostolac, Kolubara and Kosovo are of Upper Miocene (Pontian) age and are classified as humic coals of telohuminitic- detrohuminitic type with very low proportion of inertinite and high proportion of xylite (35-40 wt.-%). These coals were submitted to liquefaction in a batch reactor. According to huminite reflectance (0.24-0.30% Rr) and volatile contents (58-62%, daf), they belong to the category of soft brown coals (lignites), which contain high proportion of ash content (30-43%, dry basis). The liquefaction process was carried out in a batch reactor by passing a stream of hydrogen through a tetralin dispersion of pulverized coal (-160 µm) in the presence of granular catalyst. The effect of reaction parameters both on the yield and the nature of liquefaction products was studied with temperature ranging from 365 to 440oC, the pressure from 13.5 to 16.5 MPa and the duration of the process from 1 to 8 hours. The coals provided similar yields of the liquid reaction products. Morphographic and optical changes of the raw coal macerals were examined with microscopic analyses of the solid residues during the liquefaction process. Formation of different new grain categories was observed, which originated from insoluble or thermally changed material, depending on the experimental conditions. Twelve different categories of grains were identified and their petrographic composition and optical properties were analyzed. Low proportion of humoplasts, cenospheres and semi-coke in the solid residues indicated a high reactivity of all three examined soft brown coals in the liquefaction process. The nature of the changes observed both in the organic and the mineral components of the coal grains were used to correlate the experimental conditions with the degree of coal hydrogenation. A good reactivity of the chosen soft brown coals was also observed. High conversion degrees were observed in all three coal samples. Depending on the temperature and the residence time, the conversion degrees were found to be 84-93% (Kolubara), 80-86% (Kostolac) and 70-91% (Kosovo). Correlation of the yields with the coal petrographic changes served as a basis for the choice of optimal hydroliquefaction conditions of Serbian low rank coals.
38 th Patras 2005: 57 Annual Meeting of the ICCP
INFLUENCE OF PETROGRAPHIC COMPOSITION OF COAL ON DESORPTION AND ADSORPTION CAPACITY OF CARBON DIOXIDE AND METHANE; EXAMPLES FROM INDIANA, USA
Mastalerz, M.1, Drobniak, A.1, Rupp, J.1, Strapoc, D.2
1 Indiana Geological Survey, Indiana University, 611 North Walnut Grove, Bloomington, IN, 47405, USA ([email protected]) 2 Department of Geological Sciences, Indiana University, 1001 E. 10th St., Bloomington, IN 47405, USA
Samples of high volatile bituminous coal from several Pennsylvanian coal beds in Indiana were analyzed with regard to their quality, petrographic composition, coalbed gas content, and CH4 and CO2 adsorption capacity. The purpose of this project was to: 1) study the influence of coal petrographic composition on sorption capacity of these two gases; and 2) search for relationships between petrographic composition and the gas content present in the coal. Gas content was determined by the canister desorption technique. Multiple canisters were used at each location to sample the whole coal thickness in order to study in-seam differences between different parts of the coal beds, 3 represented by individual canisters. The coals studied can adsorb 4-6.3 m /ton of CH4 3 o and 19.5-24.6 m /ton CO2 (dry ash free basis, at temperature 17 C and pressure ~2.8 MPa). Generally coal with higher vitrinite content has higher CO2 sorption capacity, and this relationship significantly improves when only one vitrinite maceral, collotelinite, is considered. The relationship becomes weaker when inertinite is added to vitrinite, CO2 capacity also drops with increasing liptinite content. These observations suggest that collotelinite possesses the most favorable pore structure for CO2 for the coals studied. In contrast, no relationship with petrographic composition has been revealed for CH4 sorption capacity. Canister desorption experiments of the coal indicate significant in- seam variations in the gas content. For example, among six canisters housing 1.8 m thick Seelyville Coal in Gibson County, the total gas content varied from 0.8 m3/ton to 3.6 m3/ton. These in-seam variations are related to petrographic composition, ash yield, moisture content, as well as other factors, and because of this complexity are difficult to predict. Therefore, collecting adequate number of samples for canister desorption is a very important aspect of reliable gas determination for an individual coal bed.
39 th Patras 2005: 57 Annual Meeting of the ICCP
NON-CONVENTIONAL METHOD TO DETERMINE THE STRUCTURE OF THE ACTIVATED CARBON
Predeanu, G.1, Panaitescu, C.2
1 Department of Raw Materials, Metallurgical Research Institute, 060543 Bucharest, Romania ([email protected]) 2 Faculty of Industrial Chemistry, University Politehnica Bucharest, 011061 Bucharest, Romania
The wooden origin of Romanian xylites belonging to Oltenia’s Pliocene deposits involves some difficulties on combustion efficiency during utilization in the power plants. That turns to advantage during valorization on activated carbon manufacturing, due to low inorganic matter which prevents the catalytic action during gasification with steam and CO2 and structural characteristics comparable to commercial adsorbents.
The aim of the petrographic study is to characterize the structural components in xylite and chars used in activated carbon manufacturing. That provides theoretical substantiation to explain the specific behavior in the thermal processes of pyrogenation and activation. It was found out that the “useful” grain sizes higher than 10 mm with a random ash content of 2.5% (db), give the optimal material for the processes of charcoal and further activated carbon manufacturing, because of the existence of a higher portion of structured wooden constituents, with initial high porosity (fibrous + cellular textinite) and small amount of carbargilite structures. In the pyrogenetical process these structures involve the development of a high porosity, which has a favorable influence on the activation process. The structural composition of char determined by a non-conventional method is very important, because it influences the texture and porosity of the pyrogenated and activated xylite. The porous structure depends to the greater extent on the coal rank, grain size, carbonization and activation temperature and the reaction time during both processes. In the xylitic char – carbonized woody material – activation causes changes that are typical for this material: developing of pores with increasing burn-off, starting with ultra-microporosity, which is gradually transformed into micropores and then into the fraction with the narrowest mesopores. The influence of the activation temperature is similar to that of a porous carbonaceous material: for the same burn-off, the higher the activation temperature, the broader the pores that develop. As a result, taking into consideration that the organic substance of this char is suitable for activation, a comparatively uniform porous structure can be developed in the xylitic activated carbon. Apart from the significant volume of macropores, this structure is composed of very narrow pores, mainly micropores and fraction of very narrow mesopores, giving a high surface area (about 800 m2/g), pore volumes between 0-300 Å (about 0.3 cm3/g), low pore radii (about 7-8 Å) and thus, good adsorptive properties.
40 th Patras 2005: 57 Annual Meeting of the ICCP
RESEARCH ON MICROSTRUCTURAL CHARACTERISTICS OF THE TI AND QI FROM COAL TAR, COAL PITCH AND THEIR COKES
Panaitescu, C.1, Predeanu, G.2
1 Fuel Laboratory, Faculty of Industrial Chemistry, University POLITEHNICA Bucharest, str. Polizu 1, sector 1, 011061 Bucuresti, Romania ([email protected]) 2 Metallurgical Institute – ICEM, str. Mehadia 39, sector 6, 060541 Bucuresti, Romania
The interest for the composition and structure of the toluene and quinoline insoluble matter (TI, QI) in coal tar and pitch – as raw and coked material – is both scientific and practical. It can provide valuable information about: - carbonization behaviour of tar and pitch fractions and thermo-chemical process development during coal coking; - influence of TI and QI on the mesophase formation; - isotropic and anisotropic texture of coke; - utilisation of these chemical products. The paper presents the results of the research carried out in laboratory scale, in order to establish the tar composition and properties for the “special” pitches prepared. The samples of TI and QI and their cokes were analysed from the following viewpoints: - chemico-tehnical composition (contents of ash, volatile matter); - IR spectrogrammes; - X-Ray diffractogrammes; - carbopetrographical structure and composition. The last analysis was the most important for the current research. The results are given in many micrographes revealing the raw and coked samples composition and the texture of the constituents. The TI and QI insoluble matter of the raw and coked samples contain many carbonaceous inclusions in different stages of thermal transformation. Their texture depends on their nature and the carbonization temperature. An original and important result of this carbopetrographical study is represented by the possibility of identification and even determination of “β-resins”. In the pyrogenetic processing of the binder-pitches, for carbon products manufacturing, these findings may be used to establish the β-resins influence on the anisotropic texture of coke formation.
41 th Patras 2005: 57 Annual Meeting of the ICCP
PHYSICAL STUDIES OF SHUNGITE
Kwiecińska, B.1, Pusz, S.2, Krzesińska, M.2, Pilawa, B.2
1 Faculty of Geology, Geophysics and Environmental Protection, University of Science and Technology, AGH, Al. Mickiewicza 30, 30-059 Kraków, Poland ([email protected]) 2 Institute of Coal Chemistry, Polish Academy of Science, ul. Sowińskiego 5, 44-121 Gliwice, Poland
In Karelia (Russia) near Shunga village two varieties of shungite occur in Precambrian metamorphosed sediments. Both varieties are very hard and compact. They show a conchoidal fracture. The bright variety is of steel-black colour with a metallic luster, while the dull variety has a numerous accumulations of inorganic minerals (pyrite, quartz, clay, carbonates). Microscopic observations under reflected light of both varieties did not show special differences, except that bright samples were more homogeneous with a slight anisotropy visible under crossed nicols. The physical parameters such as bulk porosity, true density, optical reflectance, dynamic elastic moduli and EPR parameters, as well as the mineralogical composition (using X-ray diffractometry) were determined for both varieties of shungite. To determine the bulk porosity of shungite the apparent and true densities were measured. Dull variety has porosity 1.18% but bright samples have the value of porosity from 8.4% to 14.7%.The dynamic elastic moduli were determined from the apparent density and ultrasonic velocity measurements using an ultrasonic tester (Tester CT1, Unipan-Ultrasonic, Poland). The reflect elasticity of the studied samples is distinctly higher for dull shungite than for bright variety. Reflectance measurements were made on randomly oriented grains of shungite. For bright variety Rmax varied from 7.01- 7.15% and for dull Rmax = 5.94%. Reflectance measurements made on natural cleavage surfaces of bright shungite showed higher values equal to 9.83-11.40%. These values suggest the greater ordering of graphene layers in the case of bright shungite. X-ray analysis revealed the same tendency. Diffractograms of bright shungite are almost identical with those for semigraphite for basic reflexes (002), (101) and (004) but for dull sample are more similar to meta-anthracites or even anthracites according to the ICCP system. The studies of shungite samples by electron paramagnetic resonance (EPR) spectroscopy were performed using an X-band (9.3 GHz) EPR spectrometer (Radiopan, Poland) with magnetic modulation 100 kHz. The following parameters: amplitudes A, g factors and line widths show the differences between the two varieties of shungite. Amplitude of the first EPR line resulted from organic paramagnetic centers of bright shungite, was considerably higher than amplitude of the first EPR line of dull shungite. π electrons delocalized on large multi-ring aromatic units with g factor 2.0029 mainly exist in bright shungite. The lower amplitude of the second EPR line with g value 4.2878 was observed for bright shungite. The higher amount of Fe3+ ions responsible for the second EPR lines at 150 mT exists in dull shungite. All results described here show the differences in molecular structure and catagenetic stage of maturation, degree of graphitization of organic matter in bright and dull varieties of shungite. They could be valid and important information used in production of fullerenes.
42 th Patras 2005: 57 Annual Meeting of the ICCP
COMBINING PETROLOGICAL AND CHEMICAL APPROACHES TO SOURCE ROCK EVALUATION – A FOLLOW UP ON AN EARLY STUDY
Ranasinghe, P., Cook, A.C.
Keiraville Konsultants Pty Ltd., 7 Dallas Street, Keiraville, Wollongong, 2500 Australia ([email protected])
A multidisciplinary approach was used to evaluate the petroleum source potential of some sedimentary sequences in the Cooper-Eromanga Basin in central Australia in early 1980s, a time when organic petrologic and organic geochemical techniques were mostly used as competitive rather than complementary methods. This research study was carried out as a part of a Masters Degree programme at the University of Wollongong in Australia in association with the then Delhi Petroleum in an attempt to understand why apparently similar structures with similar source and reservoir sections varied in relation to the presence of oil reservoirs. A concept of Organic Matter Abundance Factor (OMAF) was introduced in this study for rapid semi-quantitative volumetric assessment of the organic matter content and composition for drill cuttings samples. The observed OMAF values in the cutting samples show good correlation with the solvent extractable bitumen content and the bulk chemical composition. The bulk composition of the solvent extractable bitumen shows a slight enrichment in saturates with increasing maturity as assessed from vitrinite reflectance within the oil window. A comparison was also made of some basic organic geochemical parameters of the solvent extracted bitumen with the crude oils reservoired in the sedimentary sequence indicating a local source for most of the oils. Re-examination of the study 20 years later allows the results of later drilling to be evaluated in relation to the initial study.
43 th Patras 2005: 57 Annual Meeting of the ICCP
GEOCHEMICAL AND PETROGRAPHICAL CHARACTERIZATION OF BLACK SHALES FROM IRATI AND PONTA GROSSA FORMATIONS, PARANÁ BASIN, BRAZIL
Kern, M.1, Pacheco, R.1, Engelke, V.1, Kalkreuth, W.1, Machado, G.2, Mexias, A.2, Vargas, T.2, Costa, J.2
1 Laboratório de Análises de Carvão e Rochas Geradoras de Petróleo([email protected]) 2 Laboratório de Difratometria de Raios-X; Instituto de Geociências Universidade Federal do Rio Grande do Sul Av. Bento Gonçalves, 9500 Porto Alegre CEP 91501-970 Rio Grande do Sul, Brazil
The objective of this study is the geochemical and petrographical characterization of the two main sequences of potential source rocks in the Paraná Basin, a huge intracontinental sedimentary basin located in the southeast center part of the South- American continent. The chrono-stratigraphical framework of the Paraná basin is characterized by six second order (supersequences), each of them comprising a geological record in the order of some tens of million years. Source rocks of the Ponta Grossa Formation occur in the second supersequence (Paraná, D), whereas source rocks of the Irati Formation are developed in the third supersequence (Gondwana I, Upper C - Lower Tr). The sample material was collected from outcrop locations, surface mines, and as core from exploration boreholes made in the eighties and provided by the Geological Survey of Brazil and the National Department of Mineral Production. The results of the geochemical analyses show that the rocks are composed of different types of Kerogens (I, II, III and IV) in various proportions. The total organic content (TOC) of the Irati Formation samples is high, reaching values up to 21 wt.-%, with an average value of 5 wt.-%. As for the Hydrogen Index (HI), the preliminary results indicate a great scatter, with the highest values determined in rocks collected in the São Mateus do Sul area, reaching 750 mgHC/gTOC. For the Ponta Grossa Formation, the TOC values are in general lower and reach a maximum of 2.8 wt.-%, with an average value of 0.7 wt.-%. The HI values do not show a great variation, the highest values identified were in the order of 440 mgHC/gTOC. These relatively low TOC values and HI determined for the Ponta Grossa Formation samples are probably in part due to oxidation processes at the outcrop locations. Different stages of thermal evolution were also identified based on Rock Eval Pyrolysis (Tmax oC) and Spore Coloration Index (SCI). Tmax and SCI show that most of the analyzed samples are immature, but there are certain areas, where there are in the initial stage of the mature zone. Palynofacies data show that the source rocks are composed essentially by a complex and heterogenic mixture, which can be subdivided into three distinct groups of morphological constituents: (a) Phytoclasts, (b) Palynomorphs and (c) Amorphous Organic Matter (AOM). The AOM is in general the predominant constituent reaching in the Irati Formation samples up to 90 vol.-% and in the Ponta Grossa Formation samples up to 87 vol.-%. Phytoclasts and palynomorphs in general occur in minor amounts, although a few samples are characterized by a larger input of these constituents (66 vol.- % and 46 vol.-%, respectively). SEM and XRD results show that the inorganic part of the rocks is composed mainly by clay minerals, quartz, carbonates, oxides and sulfides.
44 th Patras 2005: 57 Annual Meeting of the ICCP
MICROSCOPIC IDENTIFICATION, CLASSIFICATION AND COMPARISON OF ORGANIC MATTER COMPOSITION OF THE LATE PALAEOZOIC BLACK SHALES OF SW POLAND
Nowak, G.J.
Polish Geological Institute, Lower Silesian Branch, al. Jaworowa 19, 53-122 Wroclaw, Poland ([email protected])
At least two sapropelic horizons occur in association with the Late Palaeozoic black shales of Central Europe: The older of Late Carboniferous age is the Lower Anthracosia shale of the Intrasudetic Basin, and the younger is the well-known Zechstein Kupferschiefer occurring in both the Foresudetic Monocline and the Northsudetic Basin. The first is of lacustrine origin, while the second represents shallow marine sediment. In the case of black shales, enrichments of metals such as of Au, Cu, Zn, Pt, are of economic interest. The Kupferschiefer is commonly acknowledged as one of the most important metal source rocks worldwide, known of its copper and silver occurrences. However, in the Anthracosia shales only very poor copper mineralization occurs. These two black shales are significantly enriched in organic matter, which provide information on the sedimentary environments and conditions during diagenesis. Organic matter dispersed in these shales was studied petrographically. Detailed microscopic studies of organic material dispersed in the lower horizon of the Anthracosia Shales show that liptinite, especially alginite is the most abundant component. The secondary altered matter – the solid hydrocarbons – was also observed but they are rather rare organic components in this horizon. Organic components together with mineral matter constitute the lacustrine sapropelic association, humic association (terrestrial) and intermediary association. The character and the predominance of alginite and lacustrine sapropelic association indicate that these deposits were accumulated in an open- lacustrine zone. In general, this organic matter composition is characteristic for kerogen of type I. The measurements of vitrinite reflectance demonstrate that organic matter has reached the mature stage of oil window (Ro = 0.68-0.93%). Microscopic analyses of the Kupferschiefer revealed a mixture of three maceral groups like liptinites, vitrinites and inertinites, and other categories of organics like amorphous sapropelic mass (ASM) and solid bitumens. The commonest organic components are liptinite macerals. Bituminite and alginite predominate and are diagnostic macerals for this horizon. Percentage of bituminite locally exceeds 90%. However the rest of macerals of liptinite group (i.e. sporinite and liptodetrinite), as well as amorphous sapropelic mass, occur in significantly lower amounts. The humic organic constituents (vitrinite and inertinite) are rare components and they occur in small amounts in the Kupferschiefer horizon. Organic matter composition indicates a kerogen type II. Vitrinite reflectance of the Kupferschiefer is variable indicating low organic matter maturity (0.72-1.25%), equivalent to the oil window.
Acknowledgements. The study was supported by the Ministry of Science and Information Society Technologies – grant No. 2 P04D 078 28.
45 th Patras 2005: 57 Annual Meeting of the ICCP
ORGANIC GEOCHEMISTRY, POTENTIAL SOURCE ROCKS AND THERMAL MATURATION IN SOUTHERN DEPOCENTER (KIPOURIO – GREVENA) OF MESOHELLENIC BASIN, CENTRAL GREECE
Avramidis, P., Zelilidis, A.
Department of Geology, University of Patras, 26500 Patras, Greece ([email protected])
The study area constitutes the southern depocenter (> 4200 m) of Mesohellenic Basin and extends between Kipourio and Grevena. The Mesohellenic Basin is a middle Tertiary intermontane basin developed within the Hellenide orogen and has been studied in the past for its depositional environments, basin configuration and hydrocarbon potential. In the present paper we present additional geochemical data from outcrop samples of the southern and more hydrocarbon prone depocenter of the basin. A total number of 36 samples were analyzed using the following organic geochemistry techniques: Rock-Eval pyrolysis (36 samples), maceral analysis – vitrinite reflectance and thermal alternation index (15 samples), isolation of bitumens and liquid chromatography (9 samples) and GC-MS (9 samples). The samples were collected from deltaic deposits and submarine fan sediments of late Eocene to late Oligocene age. The results of the analysis indicate different level of organic matter maturity and different depositional environments. The TOC of the analyzed samples ranges between rich and very rich (> 1%) and the organic matter includes type II & III kerogen for the submarine fan deposits and I & II for the deltaic deposits. The organic matter is predominately gas prone for the turbiditic deposits and oil prone for the deltaic deposits (S2/S3 > 5). The thermal maturity assessed from Tmax indicates the existence of horizons into the ‘oil window’ located mainly in the deltaic and inner fan deposits. This parameter is supported by the vitrinite reflectance values, that range between early mature to mature stage. The transformation ratio (mg bitumens / g TOC) indicates the existence of samples (from deltaic deposits) in the mature level (> 100 mg/g TOC) of hydrocarbon generation. The calculation of the biomarker ratios such as pristane/phytane and pristane/n-C17, phytane/n-C18, indicate terrestrial organic matter and oxidizing conditions with one exception (sample 34), which indicates reducing conditions (marine environment). The fractionation of bitumens from the column chromatography shows asphaltenic-aromatic crude oil highly decomposed. The results of the Rock-Eval pyrolysis and the distribution of the isoprenoids support the assumption of a mixture input of organic matter, indicating oxidizing conditions mainly for the submarine fan deposits and reducing conditions for the deltaic deposits. The geochemical analyses carried out in the sediments of the southern depocenter of Mesohellenic basin and the application of the TTI (burial history) show that the hydrocarbon research has to be focused onto the late Eocene deltaic deposits that indicate mature hydrocarbon prone horizons.
46 th Patras 2005: 57 Annual Meeting of the ICCP
THE RESEARCH PROBLEMS OF ORGANIC MATTER DISPERSED IN THE CARBONIFEROUS-PERMIAN LACUSTRINE BLACK SHALES FROM THE SUDETIC BASINS (SW POLAND)
Nowak, G.J.1, Górecka-Nowak, A.2, Kwiecińska B.3
1 Polish Geological Institute, Lower Silesian Branch, al. Jaworowa 19, 53-122 Wrocław, Poland ([email protected]) 2 Institute of Geological Sciences, University of Wroclaw, ul.Cybulskiego 30, 50-205 Wrocław, Poland 3 Faculty of Geology, Geophysics and Environmental Protection, AGH – University of Science and Technology, al. Mickiewicza 30, 30-059 Kraków, Poland
Black shales are characterized by increased content of, more or less, transformed organic matter (OM) giving black colour to the rocks. The shales might originate from different natural environments. Commonly they are enriched in some elements, also metals, which often form complex compounds with organic matter. They may constitute hydrocarbon source rocks or natural ore accumulations, commonly of economic value. In the Sudety Mts. such rocks are represented, among others, by Carboniferous and Permian argillaceous, argillaceous-pelitic and argillaceous-carbonate shales, which occur in the Intrasudetic Basin (IB) and North Sudetic Basin (NSB) within horizons of lacustrine origin. Late Palaeozoic lakes were common in continental palaeo- environments. They show the presence of different types of facies associations representing diversified lacustrine sub-environments. In Sudety Mts. the Uppermost Carboniferous and Lower Permian lacustrine black shales are represented by two horizons of Anthracosia shales (in IB and NSB) and Walchia shales (only in IB). The age of the horizons of Anthracosia shales in both basins were palynologically determined in Stephanian A-C/Autunian, while palynomorphs suggest the late Autunian age of the Walchia shales. From the point of view of the present research, the most essential seems to be sediments of the open-lake facies developed as very fine-grained, dark-gray or black argillaceous or argillaceous-carbonate rocks with high content of organic/carbonaceous matter – just black shales. Origin of ore enrichment, as well as influence of organic matter in ore accumulations in the Sudetic black shales has not been studied yet. Up to now an abundance of OM in Sudetic black shales and their relationship with mineralization were not the cases of special attention. The problems were only incidentally mentioned in literature and major considerations were put on topics related with isotope and organic geochemistry. This allows concluding that the present state of investigation of OM in Sudetic Late Palaeozoic basin is insufficient. The present research arises from the necessity to fulfil the gap in the knowledge of lacustrine black shales of the IB and the NSB and in a broad sense in the whole Central Europe. The systematic research will form a basis for future investigation upon metallogenesis in these rocks. The main task of the studies is to recognize the types of organic matter in both basins and to determine their thermal maturity and character of transformations. An accomplishment of the research will give birth for an entirely innovatory stage of investigation of black shales within sedimentary sequences of Poland.
Acknowledgements. Financial support is obtained through the Ministry of Science and Information Society Technologies – grant No. 2 P04D 078 28.
47 th Patras 2005: 57 Annual Meeting of the ICCP
ORGANIC PETROLOGY AND GEOCHEMISTRY OF JURASSIC CARBONATES OF THE KARST DINARIDES (CROATIA)
Troskot-Čorbić, T., Španić, D., Rumenjak, Lj., Maričić, M., Stanković, I.
INA - Industrija nafte d.d. - Corporate Processes, Research and Development Sec., Lovinčićeva bb, 10000 Zagreb, Croatia ([email protected])
Platform carbonate deposits of the Karst Dinarides area have a stratigraphic range from Middle Triassic (or even Carboniferous in some places) to Middle Eocene, forming a belt nearly 700 km long and – after reduction by younger tectonics – 80-210 km wide. Besides the significant thickness, they are characterised by frequent lateral and vertical alternations of different facies, mostly associated with different shallow marine environments; there are also carbonate slope deposits and those representing temporarily drowned platform facies and intraplatform troughs. The Jurassic part of this carbonate succession has been subdivided into 9 megafacies units. Megafacies of mudstones and wackestones deposited in lagoon and subtidal and/or isolated and restricted lagoon/deeper subtidal areas of the inner platform (Lias, Dogger, Malm), as well as megafacies of “limestones with cherts”, deposited within intraplatform troughs with temporary or continuous connection to the open sea (Malm), are the objective of this study in a sense of detailed geochemical characterization of types of organic matter and their genetic correlation. Laminated and fine-grained limestones that contain autochthonous organic matter (kerogen and associated bitumen), as well as dolomites and limestones with pores, fissures and cavities filled with migrated bitumen were collected from localities in the wider area of Velika Kapela Mt. and from “Lemeš trough” that stretches from the vicinity of Bihać in NW Bosnia towards the south into E Lika and N Dalmatia, where Jurassic intraplatform trough were formed. The results of the analyses show the presence of the kerogen type I-II in organic-rich laminated limestones, which means, the samples investigated are considered as source rocks of very high generative potential. According to microsolubility and strong yellow to yellow-orange fluorescence effect, organic matter is a mixture of algal, bacterially degraded kerogen and migrated bitumen. Bitumen reflectance is from 0.20 to 0.30% Ro. Generally, organic matter is in the diagenetic stage of thermal transformation or reaches onset of oil generation. High percentages of organic-bonded sulphur are evidence that organic matter formation took place in marine, carbonate environment with contemporaneous sulphur incorporation in a kerogen macromolecule structure. This kind of organic facies enabled hydrocarbon generation at lower degree of thermal transformation. High degree of similarity of source rock extracts and bitumens or bituminous coatings indicates short migration phenomena.
48 th Patras 2005: 57 Annual Meeting of the ICCP
ORGANIC PETROLOGY AND GEOCHEMISTRY OF THE CRETACEOUS CARBONATES OF THE KARST DINARIDES (CROATIA)
Španić, D., Troskot-Čorbić, T., Čuljak, V., Maričić, M., Rumenjak, Lj., Stanković, I.
INA - Industrija nafte d.d. - Corporate Processes, Research and Development Sec., Lovinčićeva bb, 10000 Zagreb, Croatia ([email protected])
The Adriatic Carbonate Platform, which today constitutes the Karst Dinarides, existed from Middle Triassic to Eocene and reached its mature phase over periods of Jurassic and Cretaceous. At that time, typical shallow carbonate platform of Bahama-type was surrounded by the deep Tethys sea. During the Cretaceous, restricted lagoons and shallow intraplatform lakes favoured formation of fine-grained, laminated, organic rich carbonates (limestones and dolomitized limestones). This type of facies is most abundant during Albian- Cenomanian, Upper Santonian-Lower Campanian and Maastrichtian. Source material of the organic matter was of microbial and algal origin, which formed lamalginite and bituminite. In the deeper parts of intraplatform depressions and in slope deposits (especially during Upper Santonian and Lower Campanian transgression) some strong fluorescing telalginite (mostly cysts of dinoflagelattes) is incorporated in bituminite (or “organic-mineral groundmass”). Total organic carbon of these rocks is 2 to 20%, and kerogen is type I-II (HI = 400-850 mgHC/gTOC), which results in a good to extremely high petroleum generative potential. Kerogen is very rich in organic bonded sulfur (5- 11%), due to the depletion in heavy ions. Another interesting characteristic is the 13 enrichment in heavy stable carbon isotope (δ CPDB = 18-24‰). Dominance of phytane over pristane in alkane fraction of the rock extracts reveals anoxic condition during sedimentation.
49 th Patras 2005: 57 Annual Meeting of the ICCP
BIOAEROSOLS IN KOZANI AREA, NORTHERN GREECE, AS VIEWED BY ENVIRONMENTAL SCANNING ELECTRON MICROSCOPY
Iordanidis, A.1, Buckman, J.2, Triantafyllou, AG.1, Asvesta, A.1
1 Department of Geotechnology and Environmental Engineering, Technological Educational Institute of West Macedonia, Kila, 50100 Kozani, Greece ([email protected]) 2 Institute of Petroleum Engineering, Heriot-Watt University, Edinburgh Campus, EH14 4AS, Scotland, U.K.
Bioaerosols are known as a wide spectrum of dead or alive airborne particles of biological origin, including microorganisms and fragments of all varieties of living matter (i.e. viruses, bacteria, fungal spores, pollen, plant debris and animal matter). Bioaerosols can cause adverse effects on humans, animals and plants. In the present study airborne particles were collected from Kozani region. Kozani basin is located in the NW mountainous region of Greece and is approximately 50 km long and up to 25 km wide. Several opencast lignite mines and power plants are situated in this area. Stationary and portable collectors were placed throughout the region, covering a whole year (March 2003 to February 2004). Total suspended particles were collected on fibre-glass filters, which were analysed using Environmental Scanning Electron Microscope (ESEM). ESEM is a special type of scanning electron microscope that works under controlled environmental conditions and does not require a conductive coating on the specimen, thus providing fast results. ESEM coupled with energy dispersive X-ray analysis system (EDX) enables the determination of the chemical composition of the airborne particles. In this study, emphasis was given on the bioaerosols that were trapped in the filters. Since bacteria and viruses need special impactors in order to observe them, it was only possible to detect two kinds of bioaerosols, fungal spores and diatoms. Fungal spores were more abundant during late spring-early summer period, while diatoms were observed throughout the year. Diatoms are microscopic algae that have been presented in Earth since Cretaceous age and are often well preserved in lake and marine systems. There have been recorded in the Neogene terrestrial sediments of the Balkan region, like Kozani basin. In our study, fragments of valves and frustules of circular, elliptic and square diatoms were recognised, belonging to Centrophycae and Pennatophycae classes and Aulacoseira and Fragilaria genera. There are three possible sources for the diatoms observed in our study: i) they are recent diatoms derived from the surface soils and sediments, ii) they have come during strong air movements (episodes) from the outcrops of the opencast lignite mines or the dumping areas of the overburden rocks, where Neogene diatom-rich sediments are exposed to air, iii) they might be present in the lignite, feeding the power plant and due to their composition (biogenic silica) and small size might be released to the atmosphere as fly ash particles.
Acknowledgements: The financial support of the European Community-Access to Research Infrastructure action of the Improving Human Potential Programme, through a visit at the European Infrastructure for Energy Reserve Optimisation (EIERO, Project HPRI-CT-2001- 00173) is gratefully acknowledged. We are also indebted to Dr. Nadja Ognjanova, Bulgarian Academy of Sciences, and Dr. Anson W. Mackay, University College London, for the identification of the diatoms.
50 AUTHOR INDEX
A I Pilawa B. 42 Aleksic B.D. 38 Inaner H. 11 Predeanu G. 40,41 Aleksic B.R. 38 Iordanidis A. 50 Probierz K. 34 Alvarez D. 36 Pronina N.V. 19 Antoniadis P. 14 J Pusz S. 42 Asvesta A. 50 Jelonek I. 8 Avramidis P. 46 K R B Kalaitzidis S. 15 Radovanović M. 37 Borrego A.G. 36 Kalkreuth W. 23,44 Ranasinghe P. 43 Buckman J. 50 Karayiğit A.I. 12 Rasulov A. 26 Burger H. 23 Kern M. 23,44 Rumenjak Lj. 48,49 Komorek J. 29,30 Rupp J. 39 C Kortenski J. 9 Rusinova O.V. 28 Chatziapostolou A. 15 Kostova I. 9,18 Christanis K. 15 Kruszewska K. 8 S Ćmiel S. 32 Krzesińska M. 42 Sanei H. 31 Cook A. 43 Kuti L. 27 Serjani A. 16 Costa J. 44 Kwiecińska B. 42,47 Siavalas G. 15 Cserny T. 27 Silva M. 23 Cukalla M. 16 L Simić V. 21 Čuljak V. 49 Lorenz H. 21 Siquela E. 7 Cvetkovic O.G. 38 Španić D. 48,49 M Stamenova V. 17 D Machado G. 23,44 Stanković I. 48,49 Drobniak A. 39 Machovič V. 20,35 Stasiuk L.D. 31 Marcisz M. 34 Stefanova M. 17,33 E Maričić M. 48,49 Stojiljković D. 37 Engelke V. 44 Marinov S.P. 17 Strapoc D. 39 Ercegovac M. 21,37,38 Martínez M. 10 Stukalova I.E. 28 Mastalerz M. 39 Sýkorová I. 13,20,35 F Mavridou E. 14 Fabiańska M. 32 Mexias A. 23,44 T Fadeeva N.P. 19 Mishra S. 22 Triantafyllou A.G. 50 Fernández Dominguez I. 36 Misz M. 32,35 Troskot-Čorbić T. 48,49 Filipiak P. 8 Mizera J. 20 Finkelman R. 23 Morga R. 29,30 V Vagias D. 15 G N Vargas T. 44 Gonsalvesh L. 17 Nader E. 13 Varma A.K. 22 Goodarzi F. 25,31 Nakoman E. 11 Vasconcelos L. 7 Górecka-Nowak A. 47 Nowak G.J. 45,47 Vašíček M. 20 Grzetić I. 21 Vitorovic D. 38 O H Oikonomopoulos I. 14 W Hackley P. 10 Opluštil S. 13 Willett J. 23 Hámor T. 24 Hámor-Vidó M. 24,27 P Z Havelcová M. 20 Pacheco R. 45 Zdravkov A. 9,17,18 Holz M. 23 Panaitescu C. 40,41 Zelilidis A. 46 Papazisimou S. 15 Životić D. 21,38
51 SPONSORED BY:
LARCO G.M.M.S.A.