Botryoidal and spherulitic hematite as experimental evidence of highly acidic conditions in burning coal-waste dumps and potentially on Mars.

In the extreme setting of burning coal-waste dumps in the Upper Silesian Coal Basin in Poland, botryoidal and spherulitic hematite occurs in association with sulphates and chlorides. A series of simple experiments aimed at replicating the conditions leading to the formation of hematite spherules on the burning dumps are described. Goethite synthesised in the laboratory, mixed with various combinations of other reactants, was heated in a heating chamber or a tubular furnace. Temperature, duration of heating, water and oxygen access, and pH were experimental variables. The results show that hematite may form spherules from goethite where access to oxygen is limited and where conditions are strongly acidic. The spherulitic shape of hematite produced due to dynamically changing physicochemical conditions in the burning dumps can be an indicator of an extremely acidic environment during the closing stages of coal-waste self-heating. The conditions of hematitic-spherule formation on burning coal-waste dumps may apply in a variety of other unrelated settings, e.g., waning volcanism, sulphuric acid speleologenesis and even the formation of blueberries on Mars.

Phyllite/bentonite mixture-an alternative effective buffer material for a geological disposal of radioactive waste.

The use of phyllite (Phy) instead of quartz in mixtures with bentonite (B) is recommended as a buffer material for engineering barriers in a geological repository of nuclear waste. The recommendation is based on experimentally determined sorption properties of various Phy/B mixtures. The adsorption capacity of Phy/B mixtures (Phy/B: 75/25, 50/50, and 25/75), the removal efficacy of Eu(III) ions (an analog for fissiongenic lanthanides and actinides), and the rate of their binding reaction were studied using the batch adsorption equilibrium and kinetic experiments at different Eu(III) initial concentrations, solution pH, and solution to adsorbent (L/S) ratio. The adsorption capacity of the Phy/B mixtures increased with the increased bentonite content in the mixture depending on the L/S ratio and solution pH. The highest increase in the adsorption capacity of the Phy/B mixtures compared to phyllite was observed for the Phy/B proportions of 25/75 and 50/50. The rate of the Eu(III) adsorption was the best fitted by the pseudo-second-order kinetic model indicating that the adsorption rate was controlled by chemisorption. The Sips model provided the best correlation of the adsorption experimental data, indicative of more than one adsorption site. The results of this study show the advantage of the Phy/B mixtures in immobilizing Eu and certain fission products by combining adsorption properties of the materials.

Hydrocarbon Degradation and Microbial Survival Improvement in Response to γ-Polyglutamic Acid Application.

To improve the environmental sustainability of cleanup activities of contaminated sites there is a need to develop technologies that minimize soil and habitat disturbances. Cleanup technologies, such as bioremediation, are based on biological products and processes, and they are important for the future of our planet. We studied the potential of γ-poly glutamic acid (PGA) as a natural component of biofilm produced by Bacillus sp. to be used for the decomposition of petroleum products, such as heavy naphtha (N), lubricating oil (O), and grease (G). The study aimed to assess the impact of the use of different concentrations of PGA on the degradation process of various fractions of petroleum hydrocarbons (PH) and its effect on bacterial population growth in harsh conditions of PH contamination. In laboratory conditions, four treatments of PGA with each of the petroleum products (N, O, and G) were tested: PGA0 (reference), PGA1 (1% PGA), PGA1B (1% PGA with Bacillus licheniformis), and PGA10 (10% PGA). After 7, 28, 56, and 112 days of the experiment, the percentage yield extraction, hydrocarbon mass loss, geochemical ratios, pH, electrical conductivity, and microorganisms survival were determined. We observed an increase in PH removal, reflected as a higher amount of extraction yield (growing with time and reaching about 11% in G) and loss of hydrocarbon mass (about 4% in O and G) in all treatments of the PGA compared to the reference. The positive degradation impact was intensive until around day 60. The PH removal stimulation by PGA was also reflected by changes in the values of geochemical ratios, which indicated that the highest rate of degradation was at the initial stage of the process. In general, for the stimulation of PH removal, using a lower (1%) concentration of PGA resulted in better performance than a higher concentration (10%). The PH removal facilitated by PGA is related to the anionic homopoliamid structure of the molecule and its action as a surfactant, which leads to the formation of micelles and the gradual release of PH absorbed in the zeolite carrier. Moreover, the protective properties of PGA against the extinction of bacteria under high concentrations of PH were identified. Generally, the γ-PGA biopolymer helps to degrade the hydrocarbon pollutants and stabilize the environment suitable for microbial degraders development.

The Influence of a Fire at an Illegal Landfill in Southern Poland on the Formation of Toxic Compounds and Their Impact on the Natural Environment.

Landfill fires pose a real threat to the environment as they cause the migration of pollutants to the atmosphere and water sources. A greater risk is observed in the case of wild landfills, which do not have adequate isolation from the ground. The aim of this article is to present the results of studies on the toxicity of waste from a fire in a landfill in Trzebinia (southern Poland). Both soil and waste samples were investigated. The samples were analyzed using the GC-MS method and the leachates using ICP-OES. A total of 32 samples of incinerated waste and soil were collected. The organic compounds included naphthalene, fluorene, phenanthrene, anthracene, acenaphthene, acenaphthylene, fluoranthene, pyrene, benzo (c) phenanthrene, benzo (a) anthracene, chrysene, benzo (ghi) fluoranthene, benzo (b + k) fluoranthene, benzo (a) fluoranthene, benzo (c) fluoranthene, benzo (a) pyrene, benzo (e) pyrene, perylene, indeno[1,2,3-cd] pyrene, benzo (ghi) perylene, and dibenzo (a + h) anthracene. Among the inorganic parameters, sulfates, chlorides, arsenic, boron, cadmium, copper, lead, and zinc were taken into account. Phenanthrene reached values exceeding 33 mg/L. Fluoranthene dominated in most of the samples. Sulfates and chlorides were present in the samples in concentrations exceeding 400 and 50 mg/L, respectively. Compounds contained in burnt waste may have a negative impact on soil and water health safety. Therefore, it is important to conduct research and counteract the negative effects of waste fires.

Heavy metal- and organic-matter pollution due to self-heating coal-waste dumps in the Upper Silesian Coal Basin (Poland).

This study provides potential insight between self-heating coal-waste dumps and related environmental pollution in southern Poland. Samples collected from dumps in the Upper Silesian Coal Basin were used to quantify released contents of organic- and inorganic pollutants, i.e., polycyclic aromatic hydrocarbons (PAHs) and trace elements (Pb, Cd, Cr, Cu, Zn, Ni, Hg, As). Elevated Hg concentrations (~100-1078 mg/kg) and Pb (~600-2000 mg/kg) attest to the evaporation of these metals from deeper parts of the dumps. The acidic pH levels (3.0-4.5) may help to mobilize these elements. Pearson's correlation coefficients for samples analyzed by AAS and ICP-MS indicate a similar origin for Cd, Zn, and As. Mostly 2- and 3-ring PAHs, especially anthracene in burnt soil, dominate in the samples. Chlorinated PAHs, thiophenol, pyridines, quinolines (and derivatives) in thermally-altered samples, and waste containing pyrolytic bitumen indicate coking conditions. The high levels of Hg, Pb, and Cd, and chlorinated PAHs and nitrogen heterocycles formed or enriched during self-heating in these dumps should be deemed a significant environmental hazard. Calculating the lifetime cancer risks due to PAHs and heavy metals accumulations in the dumps are substantial, and access to these dumps should be prohibited.

Preservation of geochemical markers during co-combustion of hard coal and various domestic waste materials.

Combustion of domestic waste for heating purposes in non-adapted furnaces is a common environmental problem all over the world since it leads to significant emission of harmful substances to the atmosphere. In this project fly and bottom ash from hard coal and domestic waste co-combustion were investigated on the occurrence and distribution of geochemical markers, polycyclic aromatic hydrocarbons (PAHs), and their alkyl derivatives. Hard coal with a domestic waste admixture (paper, ethylene propylene diene rubber, tire rubber, polyethylene, polyvinyl chloride) was combusted in a certified domestic central heating furnace equipped with a control and measurement system. Fly ash was collected on glass microfiber filters inside the flue gas chimney. Raw fuels, fly and bottom ash extracts were analyzed with gas chromatography-mass spectrometry (GC-MS). Geochemical markers survived the coal/domestic waste combustion and can be identified despite the presence of other organic compounds derived from domestic waste thermal decay. The highest changes in distribution and values of geochemical ratios concern light-weight compounds, i.e. lighter n-alkanes and acyclic isoprenoids (pristane and phytane), with distinct differences between fly and bottom ash. n-Alkanes expulsion significantly decreased values of Pr/n-C17 and Ph/n-C18 ratios. Due to their high molecular weight pentacyclic triterpanes mostly retained their original distributions; however, some shifts in values of their thermal maturity ratios occurred due to artificial maturation of organic matter under the heat of combustion. PAHs diagnostic ratios showed variable utility in the indication of domestic waste admixture to hard coal combusted. The highest sensitivity was found for BaP/BghiP, MPI-1, and MPI-3 whereas Fl/(Fl + Py) rather pointed out at hard coal dominating in the fuel mixture. The addition of EPDM and tires significantly worsened the quality of combustion, which is reflected in high extract yields and the retained hard coal geochemical features such as the Pr/Ph value closest to the raw coal value.

Correction to: Investigation of organic material self-heating in oxygen-depleted condition within a coal-waste dump in Upper Silesia Coal Basin, Poland.

The original publication of this paper contains a mistake.

Investigation of organic material self-heating in oxygen-depleted condition within a coal-waste dump in Upper Silesia Coal Basin, Poland.

Self-heating occurring was studied in the Bytom coal-waste dump using petrographic, mineralogical, and organic geochemical to assess the changes induced by heating on organic material and quantify-qualify the emitted gases. The distribution of geochemical markers such as n-alkanes, alkylbenzenes, alkylcyclohexanes, phenols, sulfurous compounds, and emitted gases in the waste dump is outlined. Heating of organic material there is indicated by high vitrinite random reflectance (Rr)% values that typically characterize samples with short-chain n-alkanes, alkylbenzenes, and alkylmethylbenzenes. Contents of minerals showing minor alterations are high with ~ 90% in burned-out samples. Inside the dump where temperatures can reach up to 700-1300 °C and oxygen contents are significantly reduced, conditions favor coking. This situation is confirmed by the formation of enormous quantities of phenols and alkylbenzenes or by elevated amounts of H2 formed under low-oxygen conditions (pyrolysis). Aromatization, pyrolysis (thermal cracking), and oxidation are associated with the heating in the dump. Gases such as methane, ethane, propane, and ethylene formed during self-heating can serve as fuel for the fire inside the dump, in the process generating huge amounts of CO2.

Carbon­nitrogen compounds, alcohols, mercaptans, monoterpenes, acetates, aldehydes, ketones, SF6, PH3, and other fire gases in coal-mining waste heaps of Upper Silesian Coal Basin (Poland) - a re-investigation by means of in situ FTIR external database approach.

Coal-fire gas jets emanating from waste heaps are chemically very complex and variable mixtures, as proved by our former studies. The current paper is a result of further exploration of the GASMET FTIR system via an iterative external databases search. This allowed to pinpoint a number of subsequent chemicals, both in terms of (semi)quantitative analysis and occurrence probability (fit). Some compounds represent new finds. The most likely candidates found, with fit often >90%, are CN compounds - especially hydrogen cyanide and isocyanic acid; acetylene, various alcohols, monoterpenes, formic acid. Acetaldehyde is the most common aldehyde, followed by 2-ethylhexylaldehyde. Tetrachloroethylene quite commonly occurs, but with worse fit values. An interesting find concerns methane- and ethanethiol being enriched at a vent with an intense and cumulative sulfur (S8) mineralization. Other less frequent or worse fit compounds include arenes, COS, some alcohol derivatives, other aldehydes, hydrocarbons, nitriles (acrylonitrile), ketones, acetates, ethers, acetone, acrolein (propenal), triethylamine, and methyl metacrylate. Important and relatively frequent inorganic gas is PH3, while SF6 is very rare. However, the occurrence of the later seems to be a very important discovery: SF6 is recognized by the Intergovernmental Panel on Climate Change as the most potent greenhouse gas.

Occurrence of organic phosphates in particulate matter of the vehicle exhausts and outdoor environment - A case study.

The occurrence and concentrations of a wide range of organic phosphates (OPEs) in vehicle's exhaust (VPM), ambient air particulate matter (APM), and soil of various urban environments were researched. VPM comes from passenger cars, commercial vehicles, marine and bus engines emitted in New European Driving Cycle tests whereas APM was sampled in several sites of the Upper Silesia region (Poland). APM and VPM collected on filters and soil from the same locations as APM sampling sites were extracted with dichloromethane and extracts analyzed by gas chromatography-mass spectrometry. The OPEs found include aryl phosphates such as triphenyl phosphate (TPhP) and tricresyl phosphate (TCP), alkyl phosphates - triethyl phosphate (TEP), tripropyl phosphate (TPP), tributyl phosphate (TBP) and tri(butoxyethyl)phosphate (TBEP), and alkylchlorinated phosphates including tris-(2-chloroisopropyl) phosphate (TCiPP) and tris(2-chloroethyl) phosphate (TCEP). Occurrence and concentrations of these compounds in the PM investigated are highly variable. It was found that total concentrations in APM are directly related to traffic density in particular sites of the urban environment and a style of a vehicle driving. The highest emission of OPEs was found at a crossroad and city center sites where traffic is the densest and vehicles stops and starts are frequent. Village and residential areas were less exposed to OPEs emission. Since OPEs concentrations show exponential correlations to each other also human exposure to these compounds increases exponentially with increasing traffic density. High TEP and TBP level is tentatively proposed as an indicator of emission from petrol-fueled cars. Concentrations of OPEs in some soil are related to their emission to the air and resistance to degradation of a particular compound since only the most resistant TCiPP and TPhP were identified in soil extracts.

Environmental influence of gaseous emissions from self-heating coal waste dumps in Silesia, Poland.

Gaseous emissions from seven self-heating coal waste dumps in two large coal mining basins, Upper and Lower Silesia (Poland), were investigated by gas chromatography (GC-FID/TCD), and the results were correlated with on-site thermal activity, stage of self-heating as assessed by thermal mapping, efflorescences, and surface and subsurface temperatures. Though typical gases at sites without thermal activity are dominated by atmospheric nitrogen and oxygen, methane and carbon dioxide are present in concentrations that many times exceed atmospheric values. On average, their concentrations are 42.7-7160 ppm, respectively. These are levels considered harmful to health and show that coal waste fire can be dangerous for some years after extinction. At thermally active sites, concentrations of CH4 and CO2 are much higher and reach 5640-51,976 ppm (aver.), respectively. A good substrate-product correlation between CO2 and CH4 concentrations indicates rapid in-dump CH4 oxidation with only insignificant amounts of CO formed. Other gas components include hydrogen, and C3-C6 saturated and unsaturated hydrocarbons. Decreasing oxygen content in the gases is temperature-dependent, and O2 removal rapidly increased at > 70 °C. Emission differences between both basins are minor and most probably reflect the higher maturity of coal waste organic matter in the Lower Silesia dumps causing its higher resistance to temperature, or/and a higher degree of overburning there.

Distribution of coal and coal combustion related organic pollutants in the environment of the Upper Silesian Industrial Region.

In this study, a large sample set (276) was separated into up to 15 groups, including coal, fly ash, total particulate matter, coal wastes, river sediments, and different water types. Grouping the sample set into these categories helped to identify the typical features of combustion or water-washing and compare them using newly developed polycyclic aromatic hydrocarbon diagnostic ratios. A wide range of organic pollutants were identified in samples, including aromatic and polycyclic hydrocarbons, nitrogen-heterocycles, sulphur-heterocycles + trithiolane, and polycyclic aromatic hydrocarbons substituted with oxygen functional groups. The distribution of compounds was significantly influenced by water washing or combustion. During the self-heating of coal wastes, secondary compounds such as chlorinated aromatics (chlorobenzene, chloroanthracene, etc.) or light sulphur compounds (e.g. benzenethiol and benzo[b]thiophene) were formed (synthesised). Since these compounds are generally absent in sedimentary organic matter, their origin may be connected with high-temperature formation in burning coal dumps. These compounds should be identified as persistent organic pollutants (POPs) in the environment. The newly defined diagnostic ratios have worked well in separating samples (petrogenic and pyrogenic) and have pointed out the effect of incomplete combustion on self-heated coal waste, ash from domestic furnaces, or water washing and biodegradation of the studied compounds.

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.

Geochemical markers and polycyclic aromatic hydrocarbons in solvent extracts from diesel engine particulate matter.

Exhaust particulate from compression ignition (CI) engines running on engine and chassis dynamometers was studied. Particulate dichloromethane extracts were qualitatively and quantitatively analyzed for polycyclic aromatic hydrocarbons (PAHs) and biomarkers by gas chromatography with flame ionization detector (GC-FID) and gas chromatography-mass spectrometry (GC-MS). PAH group profiles were made and the PAH group shares according to the number of rings (2 or 3; 4; 5 or more) as well as diagnostic indices were calculated. Values of geochemical ratios of selected biomarkers and alkyl aromatic hydrocarbons were compared with literature values. A geochemical interpretation was carried out using these values and biomarker and alkyl aromatic hydrocarbon distributions. It has been shown that geochemical features are unequivocally connected to the emission of fossil fuels and biofuels burned in CI engines. The effect of the exothermic combustion process is limited to low-molecular-weight compounds, which shows that the applied methodology permits source identification of PAHs coexisting in the particulate emitted.

Sources of organic pollution in particulate matter and soil of Silesian Agglomeration (Poland): evidence from geochemical markers.

The exact input of particular sources to polycyclic aromatic hydrocarbons (PAHs) concentrations in urban and industrial agglomerations is still not well recognized. The major breakthrough is possible using geochemical markers. In the air aerosol and soil samples from areas located in the direct influence of industry/traffic in Silesian Agglomeration (Poland), PAHs and other organic compounds were analyzed, including geochemical markers (biomarkers) and polar compounds from fossil fuels and biomass. Gas chromatography (GC-FID) and gas chromatography-mass spectrometry (GC-MS) were applied to investigate the composition of particulate matter and soil extracts. The results suggest that the predominant source of PAHs is fossil fuel. The presence and distribution of steranes, pentacyclic triterpenoids (i.e., hopanes and moretanes) and alkyl PAHs point to traffic emissions and fossil fuel combustion, mainly bituminous coal for power and heat purposes, as the main source of PAHs in the region. Moreover, the presence of fossil fuel biomarker in particulate matter and soil extracts from a rural site, previously considered to be free of organic pollution, requires a cautious interpretation for PAHs results. Apart from the fossil fuel, also other sources of contamination were identified in particulate matter extracts by their markers: phenols and levoglucosan for biomass and diisopropylnaphthalenes for printing materials combustion. The absence of polar biomass combustion indicators in soil extracts might be related to their higher reactivity.

Geochemical markers of soil anthropogenic contaminants in polar scientific stations nearby (Antarctica, King George Island).

The organic contamination of Antarctic soils and terrestrial sediments from nearby of five polar scientific stations on King George Island (Antarctica) was investigated. Gas chromatography-mass spectrometry (GC-MS) was applied to find composition of dichloromethane extracts of soil and terrestrial sediments. The presence of geochemical markers, such as n-alkanes, steranes, pentacyclic triterpenoids, and alkyl PAHs, their distribution types, and values of their ratios indicates the predominating source of organic fossil fuels and products of their refining rather than from the natural Antarctic environment. Fossil fuel-originated compounds well survived in conditions of Antarctic climate over long times thus enabling to characterize geochemical features of source fossil fuel identified as petroleum expelled from kerogen II of algal/bacterial origins deposited in sub-oxic conditions and being in the middle of catagenesis. Both microbial activity and water leaching play an important role in degradation of terrestrial oil spills in the Antarctica climate, and petroleum alteration occurs lowly over long periods of time. Synthetic anthropogenic compounds found in terrestrial Antarctica sediments included diisopropylnaphthalenes, products of their sulfonates degradation in paper combustion, and organophosporus compounds used as retardants and plasticizers.

Bioelements and mineral matter in human livers from the highly industrialized region of the Upper Silesia Coal Basin (Poland).

Contents of mineral substance, silica, and a range of bioelements and toxic elements (Mg, Na, K, Ca, Ba, Zn, Cr, P Al, Cd, Mn Cu, Ni, Pb, Sr, Fe) in 38 livers of donors from the Upper Silesia Coal Basin (southern Poland) are presented. Elements were determined by inductively coupled plasma-atomic emission spectrometry (ICP-AES) with the exception of silica that was estimated colorimetrically. Concentrations, concentration variability, and correlations between selected liver components determined for the total population are related to donor age, gender, and lesion occurrence. Correlations between particular elements were found using correlation coefficient values and the Fisher transformation. Mineral substance in the livers lies in the range 0.40-5.03 wt%. With increasing donor age, mineral-matter content decreases to a minimum for the 40-60 years of age range. Microbioelement contents show a similar tendency, while microbioelements and toxic elements reach maximum contents in donors aged 60-80 years. All elements show content decreases in livers from the oldest group (>80 years). Silica contents increase with age. Variability of element contents is lowest in the older subpopulations. Livers with lesions show lower element contents and variability. The results are compared to literature data for regions of Poland assumed to be of low pollution and to data from comparable regions in Japan and Hungary. Up to our knowledge, this paper is the first work describing the total contents, as distinct from contents of selected elements, of mineral substance in human livers.

Levoglucosan and other cellulose markers in pyrolysates of Miocene lignites: geochemical and environmental implications.

Using the pyrolysis-gas chromatography-mass spectrometry and off-line pyrolysis/silylation methods for lignites from three Miocene brown coal basins of Poland resulted in the characterization of many organic compounds, including dominant cellulose degradation products such as levoglucosan, 1,6-anhydro-beta-D-glucofuranose, and 1,4:3,6-dianhydroglucopyranose. Levoglucosan is a general source-specific tracer for wood smoke in the atmosphere and recent sediments. The presence of unusually high levels of this compound in brown coal pyrolysates suggests that a portion of this compound concentration in some airsheds may originate from lignite combustion. On the other hand, nonglucose anhydrosaccharides, in particular, mannosan and galactosan, typical of hemicellulose, are not detected in those lignite pyrolysates investigated. This indicates that mannosan and galactosan are better specific tracers for combustion of contemporary biomass in those regions were the utilization of brown coals containing fossilized cellulose is important.