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A number of independent methods have been used to measure the thermal maturity of Silurian rocks from the Holy Cross Mountains in Poland. Black shales are characterized by diverse TOC values varying from 0.24-7.85%. Having calculated vitrinite equivalent reflectance using three different formulas, we propose that the most applicablevalues for the Silurian rocks are those based on Schmidt et al. (2015) equation. Based on this formula, the values range from % 0.71 VReqvVLR (the vitrinite equivalent reflectance of the vitrinite-like macerals) to % 1.96 VReqvVLR. Alternative, complementary methods including Rock Eval pyrolysis and parameters based on organic compounds (CPI, Pr/-C17, Ph/-C18, MPI1, and MDR) from extracts did not prove adequate as universal thermal maturity indicators. We have confirmed previous suggestions that Llandovery shales are the most likely Silurian source rocks for the generation of hydrocarbons in the HCM.
The Lower Palaeozoic basin at the western slope of the East European Craton (EEC) (Fig. 1) is currently recognized as one of the most interesting areas for shale gas exploration in Europe. The Upper Ordovician and/or Lower Silurian graptolitic shale is here the major potential reservoir formation (Figs. 2, 3) (Poprawa & Kiersnowski, 2008; Poprawa, 2009). Moreover, the Upper Cambrian to Tremadocian Alum shale is an additional target locally in the northern part of the Baltic Basin. These sediments are often rich in organic matter (Klimuszko, 2002; Poprawa & Kiersnowski, 2008; Więcław et al., 2010; Skręt & Fabiańska, 2009), as well as silica. Limited data from two wells in the western part of the Baltic Basin show silica contents up to 60-70% (Fig. 4) (Krzemiński & Poprawa, 2006). The advantage of the Lower Palaeozoic shale from the western slope of EEC is its broad lateral extend (Fig. 1) and relatively quiet tectonic setting. The later is particularly true in the case of the Baltic Basin and Podlasie Depression. Structural development becomes to some extent more complex in the case of the Lublin region, where the Lower Palaeozoic shale appears affected by late Famennian to early Visean block tectonics. Development of the organic rich Lower Palaeozoic shale at the western slope of EEC was controlled by several factors. Very important was here the rate of non-organic detritus deposition (Fig. 5). The other factors included organic productivity of the basin, its subsidence, relative sea level changes, basin bathymetry, geochemical conditions at the sea bottom (especially oxygenation), degree of bioturbation, presence of topographic barriers at the sea bottom, leading to development of isolated anoxic zones, sea currents configuration, and climate changes. Organic matter of the Lower Palaeozoic is characterized by presence of II type of kerogen. Appearance of the organic-rich shale within the Lower Palaeozoic section at the western slope of the EEC is diachronic (Fig. 6). From NW towards east and SE, the intervals richest in organic appear related to systematically younger strata, starting from the Upper Cambrian to Tremadocian, as well as the Upper Llanvirn and Caradoc in the Łeba Elevation (northern onshore Baltic Basin; Fig. 7). In central parts of the Baltic Basin and Podlasie Depression as well as NW part of the Lublin region, the intervals richest in organic matter are found in the Llandovery section, while in the eastern part of the Baltic Basin and SE part of the Lublin region the highest TOC contents are found in the Wenlock. Therefore, depending on location at the western slope of EEC, different formations are recognized as the targets for shale gas exploration. The Upper Cambrian to Tremadocian shale, present only in the northern part of the Baltic Basin, is characterized by very high contents of organic matter, with average value for individual sections usually ranging from 3 to 12% TOC. This shale formation is, however, of very limited thickness, not higher than several meters in the onshore part of the basin (Szymański, 2008; Więcław et al., 2010). In onshore part of the studied area, thickness of the Caradoc shale changes from a few meters up to more than 50 m (Modliński & Szymański, 1997, 2008). Contents of organic matter in these sediments are the highest in the Łeba Elevation zone and the basement of the Płock-Warszawa trough, where average TOC contents in individual well sections range from 1% to nearly 4%. Ashgill rocks are characterized by high TOC contents only in the Łeba Elevation zone, where average TOC values for individual well sections rise up to 4,5% at the most. Llandovery shale has high TOC contents, particularly in its lower part, throughout vast parts of the western slope of EEC. The maximum measured TOC contents in those rocks in Podlasie Depression are nearly 20%. Average TOC values for individual sections of the Llandovery are usually equal 1% do 2,5%, except for the Podlasie Depression, where they may reach as much as 6%. Thickness of the Llandovery shale generally increases from east to west to approximately 70 m at the most. However, in the major part of that area it ranges from 20 to 40 m (Modliński et al., 2006). Thickness of theWenlock sediments is also highly variable laterally, from less than 100 m in SE part of the Lublin region to over 1000 m in western part of the Baltic Basin. Average content of organic matter in individualWenlock sections in central and western parts of the Baltic Basin and the Podlasie Depression usually ranges from 0,5% to 1,3% TOC. In the eastern part of the Baltic Basin and in the Lublin region it is higher, rising to about 1-1,7% TOC. The above mentioned TOC values show the present day content of organic matter, which is lower than the primary one. The difference between the present and primary TOC contents increases along with increasing thermal maturity. It is also highly dependant on genetic type of kerogen. Taking into account the II type of kerogen from the analyzed sediments, it may be stated that in the zones located in the gas window the primary TOC was at least one-half greater than indicated by laboratory measurements. From the shale gas point of view, the basins at the western slope of EEC are characterized by a negative relation between depth at present day burial and thermal maturity (Poprawa & Kiersnowski, 2008). In the zones with burial depth small enough to keep exploration costs at very low level (Fig. 8), thermal maturity of shales is too low for gas generation (Figs. 9, 12a). Maturity increases westwards (Fig. 8) along with depth of burial (Fig. 9). Thus, the potential shale gas accumulations in the western part of the studied area occur at depths too high for commercial gas exploration and exploitation (Fig. 12b). Between of the zone of maturity too low for shale gas development and that where depth of burial is too large for its exploration, there occurs a broad zone of the Lower Palaeozoic shale with increased shale gas exploration potential (Fig. 13) (Poprawa & Kiersnowski, 2008; Poprawa, 2009). In that area, there are shale intervals of relatively high thickness and average TOC exceeding 1-2% TOC (Fig. 7, 10, 12c). Thermal maturity of these rocks appears sufficient for generation of gas (Fig. 9, 10), and results of well tests for deeper-seated conventional reservoirs suggest good quality of dry gas with no nitrogen (Fig. 12c). It should be noted that some gas shows have been recorded in the Lower Palaeozoic shale. Moreover, depth of burial is not too large for commercial shale gas exploration (Fig. 8, 10). Hydrocarbon shows and their composition in the Lower Palaeozoic are strictly related to thermal maturity of the source rock. In the zones of low maturity, these are almost exclusively oil shows documented. Further westwards, in the zone transitional to the gas window area, gas is wet and contains significant contribution of hydrocarbon gases higher than methane.Within the gas window zone, the records are almost exclusively limited to methane shows. Moreover, within the zones of low maturity high nitrogen contents were recorded (Poprawa, 2009). In the zones characterized by thermal maturity in the range from 0,8 to 1,1% Ro and very high TOC contents (over 15% at the most), there is a potential for oil shale exploration. The zones with the highest oil shale potential include eastern Baltic Basin in SW Lithuania and NE part of the Podlasie Depression. Some data necessary for entirely firm estimations of potential shale gas resources of the Lower Palaeozoic complex in Poland are still missing. However, preliminary estimates indicate that these shale gas resources may possibly be classified as gigantic (1,400-3,000 bln m3 of recoverable gas; Fig. 15). For comparison, resources of conventional gas in Poland are equal to 140,5 bln m exp.3, and annual domestic gas consumption is at the level of 14 bln m exp. 3. However, it should be noted that some characteristics of the Lower Palaeozoic complexes indicate increased exploration risk. The average TOC contents are here lower than in classic examples of gas shales, like e.g. Barnett shale. Moreover, in the zone of optimal burial depth (less than 3000–3500 m) thermal maturity is lower than in the case of the Barnett shale core area. An important risk factor is also both a limited amount and limited resources of conventional gas fields in the Lower Palaeozoic complex (Fig. 13). Amount and intensity of gas shows in the Lower Palaeozoic shale are also relatively low, and there is no evidences for presence of overpressure in this complex. In the eastern part of western slope of the EEC, there appears an additional risk factor-arelatively high content of nitrogen in gas.
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