Justyna Ciesielczuk

Plant occurrence on burning coal waste – a case study from the Katowice-Wełnowiec dump, Poland

Abstract Coal-waste dumps superimposed on former rubbish dump frequently undergo selfheating and selfignition of organic matter dispersed in the waste. The special conditions for plant growth generated as a result have been investigated since 2008 on the municipal dump reclaimed with coal wastes in Katowice-Wełnowiec, Poland. The plants observed most frequently where heating has occurred are Sisymbrium loeselii, Artemisia vulgaris, Sonchus arvensis, Chenopodium album, Achillea millefolium, Cirsium arvense, Amaranthus retroflexus, Atriplex nitens and Solanum nigrum. Some new, rare species such as Portulaca oleracea, first noticed in 2011, may be added. Most of encroaching species are annual, alien archeophytes and neophytes. Native species are mainly perennials. The majority of these species show a tendency to form specimens of huge size (gigantism). The abundance of emitted CO2 and nitrogen compounds is the likely cause of this. Additionally, the plants growing there are not attacked by insects. The heating of the ground liquidates the natural seed bank. After cooling, these places are seeded by species providing seeds at that very moment (pioneer species). Heated places on the dumps allow plant growth even in the middle of winter. As the seasonal vegetation cycle is disturbed, plants may be found seeding, blooming and fruiting at the same time.

Chapter 14 – Thermal Transformations of Waste Rock at the Starzykowiec Coal Waste Dump, Poland

Large dumps of coal waste are a necessary consequence of coal mining. In some cases, the waste material undergoes self-heating and combustion that changes the nature of the organic- and mineral matter of the wastes. The range of the alterations depends on the properties of the waste rocks (maceral composition and rank of organic matter) and the heating history, especially the rate and duration of heating and the degree of access for air and moisture. The Starzykowiec dump located within Chwalowice coal mine (Upper Silesia, Poland) dates from the beginning of the previous century. It contains wastes that have been thermally altered to varying degrees—reflected in colors ranging from black through yellowish, orange, red, to white and in their structure (some altered wastes are hard and solid, others soft). A coal mud collector is located on the top of the dump. Some of the waste contains organic matter both visible under a microscope and as a bituminous fraction analyzed by GC-MS. Others contain organic matter only visible under a microscope or only a bituminous fraction analyzable by GC-MS or, in some, no organic matter at all. The alterations typically seen in the wastes indicate that the temperature rose slowly; macerals show paler colors, higher reflectance, and no porosity due to devolatilization. In some waste, their yellowish color and very high reflectance indicate a very pronounced degree of alteration. In other strongly altered waste, porous, yellowish organic matter is indicative of high heating rates. Mineral-matter compositions of the waste on the Starzykowiec dump also show a wide range of thermally induced changes. There are wastes where mineral matter is unchanged and others where primary compositions are completely transformed. High-temperature mineral phases, e.g. diopside, mullite, and indialite, may be formed. On the basis of the color of powdered samples, wastes can be divided into eight groups of different mineral compositions. However, mineral phases such as gypsum and other sulfates formed due to late-stage weathering can change the chemical compositions of the waste. The organic compounds present in dichloromethane extracts, the distributions of which were determined with GC-MS, include n-alkanes, acyclic isoprenoids, pentacyclic triterpanes (hopanes and moretanes), aromatic hydrocarbons together with their C1–C5 alkyl derivatives, and PAHs from naphthalene to perylene. Relative percentage contents of PAHs, and biomarker- and alkyl-PAHs ratios allow waste organic matter composition, geochemical features, and thermal transformations caused by self-heating to be assessed. Several diagnostic changes in biomarker distributions identified include the thermal removal of lighter compounds and related changes in Pr/Ph, MNR, DNR, and TNR values, and enrichment in C31 pentacyclic compared to C30 and C29 triterpanes. Geochemical parameters were correlated to each other and to vitrinite reflectance. Results indicate that biomarker- and aromatic-hydrocarbon parameters, normally applied in the assessment of organic matter thermal maturity, show comparable patterns in the coal waste. Correlations with vitrinite reflectance and between individual geochemical parameters agree with thermal evolution trends typical of coal-waste deposits unchanged by self-heating whereas, in rocks altered by self-heating, biomarker- and aromatic-hydrocarbon parameter values approximate those characterizing overheated organic matter and coal pyrolysates.

Geochemistry and electron spin resonance of hydrothermal dickite (Nowa Ruda, Lower Silesia, Poland): vanadium and chromium

Geochemistry and electron spin resonance of hydrothermal dickite (Nowa Ruda, Lower Silesia, Poland): vanadium and chromium Geochemical analyses for trace V and Cr have been done on a representative sample of a typical hydrothermal dickite/kaolinite filling vein at Nowa Ruda. The mineralogy of the sample is comparatively simple, dickite being the principal component (ca. 91 % of the total sample). Geochemical fractionation and inductively coupled plasma-optical emission spectrometry (ICP-OES) indicate that most (> 90 % of total metal) of the V and Cr reside in the dickite. Electron Spin Resonance (ESR) shows that most (> 70 %) of the V in the dickite structure is in the form of vanadyl (VO2+) ions. A high concentration of Cr3+ is also detected in this structure by ESR. The combination of geochemical and spectroscopic tools applied to VO2+ and Cr3+ allow one to specify the Eh (> 0.4 V, highly oxidizing) and pH (≤4.0, highly acidic) of the solution during the formation of dickite from the Nowa Ruda Basin. Substantial proportions of the V and Cr (as well as VO2+ and Cr3+) in the dickite structure were probably contained in an original hydrothermal acid water. We suggest that hot hydrothermal waters leached the surrounding varieties of gabbroids enriched in V and Cr for the dickite-forming solution. The results of this work have shown V and Cr are potentially reliable indicators for geochemical characterization of the physicochemical conditions of their formation. The bulk-rock V/Cr ratio in hydrothermal dickites and kaolinites from Nowa Ruda, Sonoma (California, USA), Cigar Lake (Saskatchewan, Canada) and Teslić (Bosnia and Hercegovina) is also briefly explored here as a potential tracer of redox state during their formation.

First multi-tool exploration of a gas-condensate-pyrolysate system from the environment of burning coal mine heaps: An in situ FTIR and laboratory GC and PXRD study based on Upper Silesian materials

A methodological approach to the complex geochemical analysis of the coal fire in burning coal mine heaps (BCMH) of Upper Silesian Coal Basin has been developed. The other approach used is gas chromatography and indicatory tubes. Powder X-Ray Diffraction is applied for phase analysis to determine the species composition of mineral condensates present within and around gas flues. The gas compositions are proved to be extremely variable, when comparing both different BCMH and flues or flue zones of the same heaps. One outstanding determination concerns GeCl4, found in most samples often in large quantities. No evident dependence between the gas and mineral condensate compositions is found: N-rich condensates may but do not have to be associated with NH3-, pyridine-, or NOx-rich gases. This is also true for S-rich and Cl-rich mineralization in connection with gases of SO2, H2S, OCS, CS2, thiophene, dimethyl sulfide, dimethyl disulfide, HCl, and various halogenated hydrocarbons. Fluorine is rarely present as HF, whereas SiF4 occurs more frequently and in much larger quantities. AsH3 is mainly a trace gas but may locally be enriched. Besides the common gases, a number of trace gases is also determined based on residual FTIR spectra. Those with the highest presence chance include cyanogen isocyanate, cyanogen N-oxide, (iso)cyanic acid, c-cyanomethanimine (ethylenediimine), isocyanatomethane, iodocyanoacetylene, acetonitrile, acetaldehyde, m-hydroxybenzonitrile (m-cyanophenol), isonitrosyl chloride, nitrosyl isocyanide, difluorosilane, pentacene, triphenylene, thiazolidine, cyclohexane, and a trinitrenetriazine. The occurrence of some metals and semimetals (e.g., Al, Mg, Ga) as neutral hydroxides, suggested by other authors to occur in natural gases, is possibly confirmed. The presence of trace metal carbonyls, nitrosyls and hydrides is also possible.

Chapter 17 – Mineral Transformations and Actinide Transport: Combustion Metamorphism in the Wojkowice Coal-Waste Dump, Upper Silesian Coal Basin, Poland

Coal wastes at the Jowisz coal mine in Wojkowice, Upper Silesia, Poland were deposited on a dump, which finally covered an area of ca 7 ha containing about 1,200,000 t of wastes. Processes of self-heating changed the properties and composition of the wastes, and generated fluids and melts resulting in the formation of new mineral phases. Based on the intensity of combustion, alteration in the dump can be divided into three zones, namely, a core zone with yellow and red slates welded with slag and paralava, an aureole zone with dispersed hematite and no paralava and an external zone unaffected by combustion. Samples of different grain sizes were collected from each zone to establish the mineral transformations that have taken place and to check actinide behavior during combustion. The most intense changes characterize very fine-grained wastes and paralava. It is clear that not only temperature, but also rock type, grain size, and local conditions such as oxygen access influence on the intensity of changes in the wastes.