Magdalena Misz-Kennan

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.

Distribution of phenols related to self-heating and water washing on coal-waste dumps and in coaly material from the Bierawka river (Poland)

Abstract Several types of coal waste (freshly-dumped waste, self-heated waste and waste eroded by rain water), river sediments and river water were sampled. The aim was to identify the types of phenols present on the dumps together with their relative abundances. Gas chromatography-mass spectrometry (GC-MS) analyses of a large number of samples (234) statistically underpin the phenol distributions in the sample sets. The largest average relative contents (1.17-13.3%) of phenols occur in the self-heated samples. In these, relatively high amounts of phenol, C1- and C2-phenols reflect the thermal destruction of vitrinite. In fresh coal waste, C2- and C3-phenols that originated from the bacterial/fungal degradation and oxidation of vitrinite particles are the most common (0.6 rel.%). Water-washed coal waste and water samples contain lower quantities of phenols. In the river sediments, the phenols present are the result of bacterial- or fungal decay of coaly organic matter or are of industrial origin.

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.

Putative Late Ordovician land plants

The colonization of early terrestrial ecosystems by embryophytes (i.e. land plants) irreversibly changed global biogeochemical cycles (Berner & Kothavala, 2001; Berner et al., 2007; Song et al., 2012). However, when and how the process of plant terrestrialization took place is still intensely debated (Kenrick & Crane, 1997; Kenrick et al., 2012; Edwards et al., 2014; Edwards & Kenrick, 2015). Current knowledge suggests that the earliest land plants evolved from charophycean green algae (Karol et al., 2001) most probably during Early-Middle Ordovician times (Rubinstein et al., 2010; and references cited therein). They were represented by small nonvascular bryophyte-like organisms (Edwards & Wellman, 2001;Wellman et al., 2003; Kenrick et al., 2012). The oldest fossil evidence from dispersed spores of presumable bryophytic nature is known from aMiddle Ordovician locality (c. 470million years ago (Ma), Rubinstein et al., 2010; Fig. 1) from Argentina (Gondwana palaeocontinent). The dispersed spore fossil record also suggests that the first radiation of vascular plants probably occurred during Late Ordovician times (c. 450Ma, Steemans et al., 2009). However, unequivocal macrofossils of vascular plants appear much later, during mid-Silurian (c. 430Ma, Edwards et al., 1992). This macrofossil evidence comes from the fossil-genus Cooksonia, an early polysporangiophyte (i.e. a plant with bifurcating axes and more than one sporangium), which is considered the earliest vascular land plant (Edwards et al., 1992; Fig. 1). Further advances in knowledge about the origin and early dispersion of polysporangiophytes are needed for a better understanding of the initial plant diversification. Unfortunately, unravelling the initial steps of polysporangiophyte evolution is hindered by gaps in the fossil record of the earliest plants as well as by limitations of inference based on molecular clocks (Kenrick et al., 2012; Edwards & Kenrick, 2015). Assessing the affinities of fragmentary fossils is frequently only tentative. Most often, only partial evidence for land plant nature is visible on fossils of Silurian–Devonian age. Nevertheless, there are numerous examples in the deep-time fossil record of organisms that have been interpreted as early embryophytes even though unambiguous land plant characters were not demonstrated. For instance, Edwards & Feehan (1980) reported on some Silurian terminal sporangia and dichotomous axes interpreted as Cooksonia-type plantswith no evidence for in situ spores nor for tracheids.Wellman et al. (2003) described the first plant mesofossils with in situ spores from the Ordovician (Katian) fossil record, but the morphology of the parent plants remains unknown. More recently, Morris et al. (2011) reported on numerous fragments of LowerDevonian plants with terminal sporangia and dichotomous axes, some of them lacking preserved unambiguous land plant characters. Interestingly, some of the plants illustrated by Morris et al. (2011, pl. VI) appear closely similar to those reported in Fig. 2 (see later). Here, we document an Ordovician (Hirnantian, c. 445Ma) putative plant macrofossil assemblage. The specimens come from an Upper Ordovician locality at Zbrza in the southern Holy Cross Mountains (HCM, central Poland, SW peri-Baltica; Supporting Information Figs S1, S2, see also Notes S1). The fossils occur in mudstones of the uppermost Ordovician (Hirnantian) Zalesie Formation dated by trilobites, brachiopods and palynomorphs (Kielan, 1959; Temple, 1965; Masiak et al., 2003; Trela & Szczepanik, 2009). The age of the plant-bearing sediments is confirmed by acritarchs and chitinozoans (Notes S1). Reported evidence consists of dichotomously branched slender axes, some with terminal discoid or ovoid structures interpreted as sporangia, which could represent the earliest macrofossil occurrence of polysporangiophytes (Fig. 1). The plant fossils described herein are scattered among various fragments of coalifiedmaterial. Two branching axes broken at both ends (3 mm long9 0.1 mm wide and 2 mm long9 0.3 mm wide, respectively; Fig. 2a,b) are attributable to the fossil genusHostinella that includes vegetative isotomously branched axes. Another specimen shows a trichotomous axis division (3.2 mm long9 0.3 mm wide; Fig. 2c), a feature known to occur in some late Silurian–early Devonian plants (Gonez & Gerrienne, 2010a, b). The studied samples also yielded several probably fertile axes. A small, dichotomously branched, slender and leafless stem (1.5 mm long9 0.2 mmwide; Fig. 2d) bears terminal structures interpreted as sporangia (0.4 mm long9 0.3 mm wide; Fig. 2d). The two other fertile specimens are not branched.They consist of a short axis (1.1 mm long9 0.3 mm wide; Fig. 2e) ending either in a horizontally stretched, presumably cup-shaped, structure interpreted as a sporangium (0.8 mm long9 1.1 mm wide; Fig. 2e) or in an ovoid/hemispherical sporangium-like body (1.3 mm long9 1 mm wide; Fig. 2f). Their form, size and structure seem to be close to those observed fromCooksonia pertoni (Fig. 2e; Lang, 1937; Edwards & Feehan, 1980) and C. hemisphaerica (Fig. 2f; Edwards & Rogerson, 1979; Edwards & Feehan, 1980), respectively. Moreover, the specimen illustrated in Fig. 2(d) looks quite similar to the bifurcating axis showing the basal part of a sporangium described by Edwards et al. (2014, Fig. 3f). Within a macerated residue, we found rare trilete spores resembling the Ambitisporites avitus-dilutus (Steemans et al., 1996; Fig. 2g,h), a morphon interpreted as indicative of vascular plants (Fanning et al., 1988; Steemans et al., 2009); however the trilete marks of our specimens are not regularly formed, which casts doubts on their trilete spore nature. Interestingly, there are a variety of Ordovician spores with irregular trilete-like folds, such as Besselia nunaatica (Nøhr-Hansen & Koppelhus, 1988) that are well known from mosses and hornworts. The last important feature shown by our