Fossil Fuel Fires: A Forgotten Factor of Air Quality

*Łukasz Kruszewski*

### **Abstract**

Spontaneous fossil fuel fires, especially coal fires, are known worldwide. They occur in numerous sites, both completely natural (coal seam outcrops) and anthropogenic (burning mining waste heaps, or BMWHs). Coal and waste/barren rock fires produce gaseous emanations, acting within exhalative processes. This factor is rarely being considered as influencing quality of the atmospheric air. The paper shortly discusses most important available methods for field gas analysis, with an emphasis on a portable FTIR spectrometer. It summarizes results of gas analyses from Polish BMWHs, using a multi-tool approach. It also lists a number of additional analyses from 53 vents of these environmentally important objects, with the main purpose of enlarging the knowledge of the span of concentrations of the particular compounds. This is especially true for formaldehyde, pyridine, CO, 1,1,1-trichloroethene, 1,1-dichloroethene, cumene, SO2, and, to a lesser extent, NO2, CCl4, ethane, propane, ethene, and thiophene. The latter, and DMS, are confirmed as gaseous S source more frequent and rich than SO2.

**Keywords:** natural spontaneous coal fires, combustion gas emissions, in situ FTIR gas analysis

## **1. Introduction – fossil fuel fires**

Spontaneous fires of fossil fuels – mainly coals but also bituminous shales and oil shales – are known worldwide. They both concern natural environments and their anthropogenic analogues – burning mining waste heaps (BCWH). The CWHs are, more or less, permanent elements of the environment of coal basins. Although sometimes under reclamation, their recultivation procedures may also negatively influence the surroundings. The phenomena taking place in the BCWH are described, e.g., in Nasdala & Pekov [1], Cebulak et al. [2], Sokol et al., [3], Stracher [4], and papers of Ł.K. The later largely characterize complex products of gaseous emissions related to both coal and barren rock – mutually known as mining waste – burning. This chapter characterizes the composition of these emissions, by juxtaposing published concentrations and their related mean values with new data obtained for new BCWH-type object. As such, the chapter extends knowledge about the geochemical charge of the BCWH gaseous emissions and, as such, their potential atmospheric input.

### **2. Environmental gas emission measurement methods**

Numerous methods of gas analysis in the environment exist. One of the most simple one, based on colorimetric chemical reactions, uses indicatory tubes (IT). This method is based on colorimetric interaction of measured gaseous species with a chemical filler. In particular, Dräger tubes allow to detect and measure amounts of gases like O2, CO2, CO, NO2, SO2, NH3, PH3 (phosphine), acetic acid, acetone, propane, benzene, toluene, styrene, *o*-xylene, butadiene, total mercaptans (thiols), methanol, *i*-propanol, trichloroethene (TCE), vinyl chloride, methyl *tert*-butyl eter (MTBE), and others. However, the IT method brings large errors due to crosssensitivity and numerous coincident reactions of the emanation-contained gaseous species, and humidity. Positive determinations for the BCWHs gases were thus single, and the following substances were observed (with semi-quantitative due to the above factors): H2S (up to 1140 ppm), HCN (single determination (s.d.), 16 ppm), acetaldehyde (possibly up to 1150 ppm), diethyl ether (up to 1100 ppm), trimethylamine (and/or other amines; ca. 57 ppm), ethyl formate (s.d., <23 ppm), and I2 (s.d., 1.7 ppm). Gas Chromatography (GC) is a method of choice for the analysis of environmental organics. A sample is put into specialized columns, where retention time of a particular molecule, related to its mass and charge (*m*/*z* parameter), is measured. However, it is relatively rarely used for gas analysis due to a need of a more sophisticated sample loader. This is overcame by a method of Colman et al. [5], where a sample sucked into a steel can and sent to laboratory (here: overseas) is reheated (to the temperature measured *in situ*), divided into aliquots with various pre-treatments including (1) passing heated aliquots over a glass for low-volatile compounds exerting and (2) water-immersion-driven revolatization, and (3) chromatographic separation. Analyses of such portioned sample using 3 detection methods: Mass Spectrometry (MS), Flame Ionization (FI), and Electron Capture (EC), both shown in Kruszewski et al. [6] and this chapter, proven to be problematic, as explained below.

induce three types of mineral-forming phenomena: a high-temperature solid–solid and gas–solid transformation of the waste, known as pyrometamorphism (up to 1200°C in the coal case; [3]); medium-temperature exhalative processes; and lowtemperature supergene weathering processes ([6, 10–12], and references therein). Of the Air Quality interest is, of course, the second group of processes, involving both gas emission and gas-waste interface reactions. The latter include direct gas desublimation (condensation) and pneumatolysis-like gaseous extraction of various waste-contained metals followed by hydrothermal mineralization. The first process mainly produces minerals like native sulfur (S8), salammoniac (NH4Cl), and a number of less frequent species like kremersite, (NH4,K)2[FeCl5(H2O)] and other chlorides. The second one is responsible for vast, thick sulfate crusts mainly comprising godovikovite-sabieite solid solution, (NH4)(Al,Fe)(SO4)2, millosevichitemikasaite solid solution, (Al,Fe)2(SO4)3, steklite, KAl(SO4)2, tschermigite, (NH4)Al (SO4)212H2O (natural ammonium aluminum alum), alunite-supergroup minerals, and many others. Pyrometamorphic processes and their product in Polish BCWH – within both the Upper and Lower Silesian Coal Basins (USCB and LSCB, respectively) was extensively studied, e.g., by Kruszewski [13, 14] and Kruszewski et al. [15, 16], with process imitation experiments described, e.g. by Kruszewski [10]. Mineralogy of the exhalative processes and gas phase composition of the local fumaroles was largely addressed by Kruszewski [6, 12, 17–19]. Fabiańska et al. [20] and Lewińska-Preis et al. [21] addressed some environmental aspects of the gas emissions in question. Supergene mineralogy was described in Kruszewski [11]. Presentation of the BCWH as models of various natural environments, including extraterrestrial ones, was shown by Kruszewski et al. [22, 23]. Biological aspects of the BCWH environment were brought up by Kruszewski & Matlakowska [24]. The fumaroles bear numerous minerals rich in trace and toxic elements, like zinc, copper, nickel, arsenic, thallium, lead, bismuth, selenium, bromine, iodine, indium, silver, and others. The mineral segregations are, obviously, related to the gas phase composition. Analyzing the latter was somewhat pioneering, as we could not find any literature sources showing the use of a portable FTIR (Fourier-Transformed InfraRed) spectroscopy for *in situ* analyzing of gaseous emissions, at least in the BCWH or the coal-fire environment in general. The IR method is a type of spectroscopy where vibrations of chemical bonds in molecules are being addressed, and depicted by their interaction with IR laser (a similar method is Raman spectroscopy). Various types of vibrations (i.e., stretching, bending, rocking, and other types) are responsible for various peaks in the spectra observed. Most compounds show response to the IR light (i.e., IR laser), by a pattern more or less characteristic for the particular molecule. Some exceptions include H2S (hydrogen sulfide), which – in the variation of the IR method described here – gives only weak signals, thus making the aforementioned IT method somewhat more useful. The main components were shown (in [6]) to be H2O and CO2, with minor but variable add of CH4 and CO. However, the composition was shown to be much more complex. The portable FTIR GASMET DX-4000 (OMC ENVAG) system was thoroughly characterized in Kruszewski et al. [6, 12]. It system a tool of choice for analysis of complex, hot, chemically aggressive and char- and ash-rich emanations, including combustion/exhaust gases. It comprises a probe with stainless-steel tip, connected with special wires with gas conditioning system (with a pressure control, pump, and system of 2 μm filters for catching any solid and liquid contaminants) and then the FTIR spectrometer. The interferometer has a ZnSe beam splitter; the sample cell has its path length of 5.0 m, volume is 0.4 L; Viton gaskets, MgF2 protective coating, and BaF2 window are present, too. The whole sampling system is internally coated by protective

*Fossil Fuel Fires: A Forgotten Factor of Air Quality DOI: http://dx.doi.org/10.5772/intechopen.96294*

layers of rhodium and, gold and nickel.

**231**

The GC method is, however, useful in the environmental gas analyses if coupled with tools like Nitrogen-Phosphorus-Detector and cryo-focusing. A good example is a work of Wickenheiser et al. [7], who analyzed gases emitted from Italian wetland bogs. The compounds included PH3, ethane, ethene, and NOx. GC coupled with Inductively Coupled Plasma – Mass Spectroscopy (ICP-MS) allowed them to address heavy organo(semi/non)metallic gases like trimethylarsine (TMA), (CH3)3As, and trimethylstibine (TMS), (CH3)3Sb, and also metallic Hg, emitted from algal mats. The same method allowed to Feldmann et al. to detect (via cryotrapping) trimethylbismuthine, (CH3)3Bi, as a common gas in municipal solid waste and sewage gas. Traces of tetramethyltin and TMS were also detected this way (*vide* [8]). Another method mentioned by the latter author is hydride generation. The use of tedlar bags, a gas trapping solution (with HNO3 and H2O2), charcoal sorbent tubes, preconcentrators, and analysis with GC–MS and GC-PID (GC with photoionization detection) is also widely exploited, e.g., to measure TMA and propanethiol [9]. A method to be exploited by the author (Ł.K.) is a GC in conjunction with Atomic Emission Spectroscopy (AES). This two-step method involved very-low-detection-limit analysis, both qualitative and quantitative, of mainly (semi)metals in a gas sample, followed by analysis of their immediate surroundings for proposing types of organic and inorganic (semi)metal forms (R. Stasiuk, *pers. comm.*).

## **3. Mining waste heaps and products of their fires**

A large number of coal mining waste heaps bear numerous spontaneous fire foci. In these burning coal-mining waste heaps (BCWHs), the fire incidents are due to criss-crossing influence of coal petrography (i.e., maceral composition), sulfide mineral content (especially pyrite), coal rank, and microbial activity. The fires

### *Fossil Fuel Fires: A Forgotten Factor of Air Quality DOI: http://dx.doi.org/10.5772/intechopen.96294*

This method is based on colorimetric interaction of measured gaseous species with a chemical filler. In particular, Dräger tubes allow to detect and measure amounts of gases like O2, CO2, CO, NO2, SO2, NH3, PH3 (phosphine), acetic acid, acetone, propane, benzene, toluene, styrene, *o*-xylene, butadiene, total mercaptans (thiols), methanol, *i*-propanol, trichloroethene (TCE), vinyl chloride, methyl *tert*-butyl eter (MTBE), and others. However, the IT method brings large errors due to crosssensitivity and numerous coincident reactions of the emanation-contained gaseous species, and humidity. Positive determinations for the BCWHs gases were thus single, and the following substances were observed (with semi-quantitative due to the above factors): H2S (up to 1140 ppm), HCN (single determination (s.d.), 16 ppm), acetaldehyde (possibly up to 1150 ppm), diethyl ether (up to 1100 ppm), trimethylamine (and/or other amines; ca. 57 ppm), ethyl formate (s.d., <23 ppm), and I2 (s.d., 1.7 ppm). Gas Chromatography (GC) is a method of choice for the analysis of environmental organics. A sample is put into specialized columns, where retention time of a particular molecule, related to its mass and charge (*m*/*z* parameter), is measured. However, it is relatively rarely used for gas analysis due to a need of a more sophisticated sample loader. This is overcame by a method of Colman et al. [5], where a sample sucked into a steel can and sent to laboratory (here: overseas) is reheated (to the temperature measured *in situ*), divided into aliquots with various pre-treatments including (1) passing heated aliquots over a glass for low-volatile compounds exerting and (2) water-immersion-driven revolatization, and (3) chromatographic separation. Analyses of such portioned sample using 3 detection methods: Mass Spectrometry (MS), Flame Ionization (FI), and Electron Capture (EC), both shown in Kruszewski et al. [6] and this chapter, proven to be

*Environmental Sustainability - Preparing for Tomorrow*

The GC method is, however, useful in the environmental gas analyses if coupled with tools like Nitrogen-Phosphorus-Detector and cryo-focusing. A good example is a work of Wickenheiser et al. [7], who analyzed gases emitted from Italian wetland bogs. The compounds included PH3, ethane, ethene, and NOx. GC coupled with Inductively Coupled Plasma – Mass Spectroscopy (ICP-MS) allowed them to address heavy organo(semi/non)metallic gases like trimethylarsine (TMA), (CH3)3As, and trimethylstibine (TMS), (CH3)3Sb, and also metallic Hg, emitted from algal mats. The same method allowed to Feldmann et al. to detect (via cryotrapping) trimethylbismuthine, (CH3)3Bi, as a common gas in municipal solid waste and sewage gas. Traces of tetramethyltin and TMS were also detected this way (*vide* [8]). Another method mentioned by the latter author is hydride generation. The use of tedlar bags, a gas trapping solution (with HNO3 and H2O2), charcoal sorbent tubes, preconcentrators, and analysis with GC–MS and GC-PID (GC with photo-

A large number of coal mining waste heaps bear numerous spontaneous fire foci. In these burning coal-mining waste heaps (BCWHs), the fire incidents are due to criss-crossing influence of coal petrography (i.e., maceral composition), sulfide mineral content (especially pyrite), coal rank, and microbial activity. The fires

ionization detection) is also widely exploited, e.g., to measure TMA and propanethiol [9]. A method to be exploited by the author (Ł.K.) is a GC in conjunction with Atomic Emission Spectroscopy (AES). This two-step method involved very-low-detection-limit analysis, both qualitative and quantitative, of mainly (semi)metals in a gas sample, followed by analysis of their immediate surroundings for proposing types of organic and inorganic (semi)metal forms

**3. Mining waste heaps and products of their fires**

problematic, as explained below.

(R. Stasiuk, *pers. comm.*).

**230**

induce three types of mineral-forming phenomena: a high-temperature solid–solid and gas–solid transformation of the waste, known as pyrometamorphism (up to 1200°C in the coal case; [3]); medium-temperature exhalative processes; and lowtemperature supergene weathering processes ([6, 10–12], and references therein). Of the Air Quality interest is, of course, the second group of processes, involving both gas emission and gas-waste interface reactions. The latter include direct gas desublimation (condensation) and pneumatolysis-like gaseous extraction of various waste-contained metals followed by hydrothermal mineralization. The first process mainly produces minerals like native sulfur (S8), salammoniac (NH4Cl), and a number of less frequent species like kremersite, (NH4,K)2[FeCl5(H2O)] and other chlorides. The second one is responsible for vast, thick sulfate crusts mainly comprising godovikovite-sabieite solid solution, (NH4)(Al,Fe)(SO4)2, millosevichitemikasaite solid solution, (Al,Fe)2(SO4)3, steklite, KAl(SO4)2, tschermigite, (NH4)Al (SO4)212H2O (natural ammonium aluminum alum), alunite-supergroup minerals, and many others. Pyrometamorphic processes and their product in Polish BCWH – within both the Upper and Lower Silesian Coal Basins (USCB and LSCB, respectively) was extensively studied, e.g., by Kruszewski [13, 14] and Kruszewski et al. [15, 16], with process imitation experiments described, e.g. by Kruszewski [10]. Mineralogy of the exhalative processes and gas phase composition of the local fumaroles was largely addressed by Kruszewski [6, 12, 17–19]. Fabiańska et al. [20] and Lewińska-Preis et al. [21] addressed some environmental aspects of the gas emissions in question. Supergene mineralogy was described in Kruszewski [11]. Presentation of the BCWH as models of various natural environments, including extraterrestrial ones, was shown by Kruszewski et al. [22, 23]. Biological aspects of the BCWH environment were brought up by Kruszewski & Matlakowska [24].

The fumaroles bear numerous minerals rich in trace and toxic elements, like zinc, copper, nickel, arsenic, thallium, lead, bismuth, selenium, bromine, iodine, indium, silver, and others. The mineral segregations are, obviously, related to the gas phase composition. Analyzing the latter was somewhat pioneering, as we could not find any literature sources showing the use of a portable FTIR (Fourier-Transformed InfraRed) spectroscopy for *in situ* analyzing of gaseous emissions, at least in the BCWH or the coal-fire environment in general. The IR method is a type of spectroscopy where vibrations of chemical bonds in molecules are being addressed, and depicted by their interaction with IR laser (a similar method is Raman spectroscopy). Various types of vibrations (i.e., stretching, bending, rocking, and other types) are responsible for various peaks in the spectra observed. Most compounds show response to the IR light (i.e., IR laser), by a pattern more or less characteristic for the particular molecule. Some exceptions include H2S (hydrogen sulfide), which – in the variation of the IR method described here – gives only weak signals, thus making the aforementioned IT method somewhat more useful. The main components were shown (in [6]) to be H2O and CO2, with minor but variable add of CH4 and CO. However, the composition was shown to be much more complex. The portable FTIR GASMET DX-4000 (OMC ENVAG) system was thoroughly characterized in Kruszewski et al. [6, 12]. It system a tool of choice for analysis of complex, hot, chemically aggressive and char- and ash-rich emanations, including combustion/exhaust gases. It comprises a probe with stainless-steel tip, connected with special wires with gas conditioning system (with a pressure control, pump, and system of 2 μm filters for catching any solid and liquid contaminants) and then the FTIR spectrometer. The interferometer has a ZnSe beam splitter; the sample cell has its path length of 5.0 m, volume is 0.4 L; Viton gaskets, MgF2 protective coating, and BaF2 window are present, too. The whole sampling system is internally coated by protective layers of rhodium and, gold and nickel.

FTIR results obtained for total 52 fumaroles in four BCWHs located in Pszów, Rybnik-Rymer, Radlin, and Rydułtowy (USCB), respectively, showed up to [in ppm, unless noticed; whole-range maximums underlined]: H2O 57.5, 19.3, 12.5, 36.2 vol.%; CO2 67.2, 7.63, 6.82, 30.6 vol.%; CO 2690, 694, 21, 347; NO 434, 38, 123, 151; N2O not observed (n.o.), 0.42, 1.2, 8.7; NO2 16430, 116, 24, 191; NH3 1715, 646, 14, 98; SO2 582, 74, 64, 226; HCl 58, 23, 2.4, 8.9; CCl4 22, 1.5, 6.0, 14; HF 4.0, 2.2, n. o., 5.1; SiF4 1890, 228, 504, 1980; AsH3 8.2, 0.49, 0.18, 0.64; CH4 82970, 1050, 838, 888; ethane 511, 306, 42, 316; propane 1446, 100, 16, 284; hexane 921, 123, n.o., 262; ethene 92, 28, 21, 21; dichloromethane (DCM) 5472, 1730, 241, 1980; 1,1-dichloroethane (1,1-DCE) 2110, 580, 175, and 742; 1,2-DCE 573, 28, 7.4, n.o.; 1,1,1 trichloroethane (1,1,1-TCE) 7.7, n.o., 40, 23; 1,2-dichloropropane (1,2-DCP) 4900, 12, n.o., 44; 1,1-dichloroethene (1,1-DCEe) 51, 3.3, 34, 140; vinyl chloride 1700, 809, n.o., 1980; chlorobenzene 416, 71, 92, 100; cumene (*i*-propylbenzene) 194, 84, 35, 75; phenol 43, 348, 37, and 103; *o*-cresol (2-methylphenol) 1620, 99, n.o., 99; furan 27, 29, 130, 12; tetrahydrofuran (THF) 598, 372, n.o., 2830; thiophene 781, 578, 773, 550; acetic acid 7000, 12, 12, 650; dimethyl sulfide (DMS) 6650, 2230, n.o., 6780; dimethyl disulfide (DMDS) 518, 36, n.o., 97; formaldehyde 5.7, n.o., n.o., and 3.1. Pyridine was observed only in Radlin, in very constant amounts, 10–11 ppm. Although certified (as in the case of other compounds in the calibration library), the maximum contents of germanium tetrachloride, GeCl4, i.e., 3130, 209, 333, and 2098 should be treated with care due to possible coincidence as yet unresolvable by the Calcmet software. Geometric means of the concentration values (Pszów, Rybnik-Rymer, Radlin, Rydułtowy, whole series) are: H2O 31, 12, 3.0, 21, and 19 (*n*total = 46); CO2 31, 4.0, 0.22, 11, and 7.0 (*n*total = 50) [vol.%]; CO 84, 186, 9.6, 81, and 81 (*n*total = 41); NO 87, 15, 14, 66, and 42 (*n*total = 24); NO2 334, 38, 14, 42, and 41 (*n*total = 26); N2O -, 0.10, 0.66, 4.3, and 0.83 (*n*total = 17); NH3 287, 22, 3.4, 59, and 88 (*n*total = 18); SO2 110, 18, 17, 48, and 56 (*n*total = 31); HCl 7.4, 4.2, 0.56, 3.0, and 3.8 (*n*total = 46); CCl4 3.2, 0.18, 0.91, 2.5, and 1.6 (*n*total = 51); HF 4.0, 2.2, , 3.3, and 3.4 (*n*total = 9); SiF4 16, 114, 94, 182, and 65 (*n*total = 29); AsH3 1.1, 0.19, 0.17, 1.0, and 0.58 (*n*total = 26); CH4 1945, 500, 23, 537, and 457 (*n*total = 47); ethane 46, 114, 15, 75, and 59 (*n*total = 37); propane 148, 70, 16, 27, and 46 (*n*total = 27); hexane 160, 25, , 15, and 38 (*n*total = 26); ethene 7.9, 7.3, 11, 8.3, and 8.2 (*n*total = 28); DCM 230, 119, 160, 295, and 214 (*n*total = 45); 1,1-DCE 235, 190, 98, 99, and 139 (*n*total = 32); 1,2-DCE 153, 28, 7.4, , and 91 (*n*total = 9); 1,1,1-TCE 5.4, , 40, 9.5, and 7.7 (*n*total = 19); 1,2-DCP 1038, 5.7, , 20, and 166 (*n*total = 9); 1,1-DCEe 19, 2.6, 31, 25, and 20 (*n*total = 35); vinyl chloride 329, 38, , 394, and 289 (*n*total = 32); chlorobenzene 24, 36, 92, 32, and 32 (*n*total = 12); cumene 28, 30, 35, 15, and 22 (*n*total = 38); phenol 14, 36, 3.8, 32, and 19 (*n*total = 32); *o*-cresol 115, 21, , 99, and 73 (*n*total = 15); furan 11, 9.8, 72, 12, and 31 (*n*total = 18); THF 126, 372, , 643, and 195 (*n*total = 10); thiophene 251, 200, 90, 156, and 186 (*n*total = 40); formaldehyde 3.5, , , 0.54, and 0.82 (*n*total = 8); acetic acid 189, 6.6, 8.1, 83, and 54 (*n*total = 22); DMS 517, 433, , 921, and 533 (*n*total = 16); DMDS 68, 11, , 31, and 41 (*n*total = 35); and pyridine -, , 11, , and 11 (total 8 records).

here. In turn, we have later used a second and third mode of the FTIR spectra reading. The first one is an external library search, where the spectra are read and calculated using libraries containing other compound sets, thus reporting semi-

Any misfits are due to recording the standards in different conditions than in the DX-4000 calibration library case. Applying this method allowed to detect additional compounds for the previously listed 4 BCWH sites [in ppm, with results for fit ≥90%, 75–90%, 50–75%, and < 50%, and whole-data maximums underlined]: acetylene, C2H2 (up to 0.81; up to 27; up to 38; up to 288), *n*-butane (; ; 7.1; 1.5), *i*-butane (; ; 9.7; 0.25), propene (; ; up to 101; up to 30), *n*-pentane (; ; 4.0; 1.9), *i*-pentane (; ; 11; 0.91), heptane (; ; up to 2.1; ), octane (; ; up to 2.3; ), nonane (; ; up to 2.1; ), decane (; ; up to 2.0; ), undecane (; ; up to 2.0; ), 1,3-butadiene (3.2; ; up to 144; up to 169), cyclohexane (; ; up to 2.7; ), α-pinene (; ; up to 4.0; up to 1.1), limonene (C10H16; ; ; up to 4.9; 2.7), 3-carene (C10H16; 512; up to 2.2), benzene (8.8; up to 5.1; up to 52; up to 5700), toluene (; ; up to 74; up to 18), styrene (; 88; 0.76; up to 154), *m*-xylene (; ; 19; up to 51), *p*-xylene (; ; 16; up to 23), ethylbenzene (; ; ; up to 8.4), 1,3,5- TMB (; ; up to 729; up to 32), 1,2,4-TMB (; ; up to 1610; up to 27), 1,2,3-TMB (; ; up to 1360; up to 23), tetrachloroethene (; up to 4.3; up to 28; up to 27), methanol (11; 5.4; up to 18; up to 75), ethanol (16; 5.4; up to 38; up to 126), *i*propanol (isopropanol; ; ; ; up to 16), *i*-butanol (isobutanol; ; ; ; 5.4), *n*propanol (; ; 982; ), methanethiol (methylmercaptan), CH3SH (; ; ; up to 55), ethanethiol (ethylmercaptan), C2H5SH (; ; 2500; up to 14), HCN (up to 8.4; up to 16; up to 88; up to 65), acrylonitrile (prop-2-enenitrile, CH2 = CHCN; ; 6.0; up to 63; up to 82), isocyanic acid (; ; ; up to 717), formic acid, HCOOH (3.0; 8.7; up to 29; up to 48), trimethylamine, (C2H5)3N (; ; ; up to 1.5), acetaldehyde (up to 45; up to 97; up to 1810; up to 6270), propionaldehyde (propanal), (C2H5)CHO (; ; ; up to 24), 2-ethylhexylaldehyde (C4H9CH(C2H5)CHO; ; ; up to 342; ), acrolein (propenal, CH2 = CHCHO; ; 1.6; up to 57; up to 25), acetone (propan-2-one) (; ; ; up to 98), methyl ethyl ketone (MEK, or butan-2-one), CH3C(O)C2H5 (; ; ; up to 28), methyl isobutyl ketone (MIBK, or 4 methylpentan-2-on), (CH3)2C2H3C(O)CH3 (; ; ; up to 2.6), diethylether (ethoxyethane, (C2H5)2O; ; ; 1.7; up to 24), MTBE (; ; ; up to 9.4), 2 ethoxyethanol, (C2H5)O(CH2)O(C2H5) (; ; up to 47; up to 32), 2-ethoxyethyl acetate (; ; ; up to 19), butyl acetate (; ; ; up to 15), 2-(2-butoxyethoxy) ethyl acetate (; ; ; up to 13), methyl metacrylate (methyl 2-methylprop-2 enoate; ; ; ; up to 10), PH3 (phosphine; ; up to 43; up to 144; up to 152), COS (up to 0.88; up to 6.1; up to 0.40; ), and last but not least SF6 (; ; up to 1.6; up to 1.5). The last compound is environmentally very important, as it is said – by the Intergovernmental Panel on Climate Change – to be the most potent greenhouse gas [25]. The measured BCWH emanation concentrations are also much higher (over 170000 times) than the highest ones measured at Mauna Loa fumaroles [26]. Calculated geometric means (whole series; with values for fit ≥50% in the parentheses): 13 (2.3) for acetylene (*n* = 14 (31)), 25 (51) for propene (*n* = 9 (3)), 17 (29) for 1,3-butadiene (*n* = 15 (5)), 0.76 for α-pinene (*n* = 6), 3.5 for limonene (*n* = 3), 6.2 for 3-carene (*n* = 4), 55 (9.7) for benzene (*n* = 34 (14)), 7.4 (21) for toluene (*n* = 11 (3)), 9.6 for styrene (*n* = 9), 9.9 (10) for *m*-xylene (*n* = 11 (8)), 13 for *p*-xylene (*n* = 7), 13 (13) for 1,3,5-TMB (*n* = 11 (8)), 11 for 1,2,4-TMB (*n* = 10), 4.5 for 1,2,3- TMB (*n* = 6), 15 (5.5) for methanol (*n* = 24 (4)), 32 (8.6) for ethanol (*n* = 26 (7)), 6.9 for *i*-propanol (*n* = 7), 23 for ethanethiol (*n* = 4), 4.2 (1.4) for tetrachloroethene (*n* = 31 (9)), 7.2 (5.9) for HCN (*n* = 47 (33)), 293 for isocyanic acid (*n* = 18), 1.2 for trimethylamine (*n* = 3), 47 (47) for acrylonitrile (*n* = 12 (9)), 15 (12) for formic acid (*n* = 35 (7)), 62 (28) for acetaldehyde (*n* = 50 (45)), 9.4 for propionaldehyde

, in %), as described in Kruszewski et al. [12].

quantitative results with fit factor (r2

*Fossil Fuel Fires: A Forgotten Factor of Air Quality DOI: http://dx.doi.org/10.5772/intechopen.96294*

**233**

GC results were also published in the paper, with confirmed occurrence of carbonyl sulfide, COS, carbon disulfide, CS2, freons (CCl3F, CCl2F2, CHClF2), *i*butane, *n*-butane, *i*-pentane, *n*-pentane, *n*-hexane, *n*-heptane, *n*-octane, *n*-nonane, *n*-decane, propene, 1-butene, *i*-butene, *trans*- and *cis*-2-butene, *trans*- and *cis*-2 pentene, ethyne, 1,3-butadiene, isoprene (2-methyl-1,3,-butadiene), 2,3 dimethylbutane; 2- and 3-methylpentanes; benzene, toluene, *m*/*p*- and *o*-xylenes, styrene, ethylbenzene, *n*- and *i*-propylbenzene; 2-, 3,- and 4- (or *m*-, *p*- and o-) ethyltoluene; 1,2,3-, 1,2,4-, and 1,3,5-trimethylbenzenes; and α- and β-pinene. As shown in the paper, the GC results may be quite unreliable due to their non-*in situ* character and possible intra-gas and gas-steel interactions, and are thus not resumed

FTIR results obtained for total 52 fumaroles in four BCWHs located in Pszów, Rybnik-Rymer, Radlin, and Rydułtowy (USCB), respectively, showed up to [in ppm, unless noticed; whole-range maximums underlined]: H2O 57.5, 19.3, 12.5, 36.2 vol.%; CO2 67.2, 7.63, 6.82, 30.6 vol.%; CO 2690, 694, 21, 347; NO 434, 38, 123, 151; N2O not observed (n.o.), 0.42, 1.2, 8.7; NO2 16430, 116, 24, 191; NH3 1715, 646, 14, 98; SO2 582, 74, 64, 226; HCl 58, 23, 2.4, 8.9; CCl4 22, 1.5, 6.0, 14; HF 4.0, 2.2, n. o., 5.1; SiF4 1890, 228, 504, 1980; AsH3 8.2, 0.49, 0.18, 0.64; CH4 82970, 1050, 838, 888; ethane 511, 306, 42, 316; propane 1446, 100, 16, 284; hexane 921, 123, n.o., 262; ethene 92, 28, 21, 21; dichloromethane (DCM) 5472, 1730, 241, 1980; 1,1-dichloro-

ethane (1,1-DCE) 2110, 580, 175, and 742; 1,2-DCE 573, 28, 7.4, n.o.; 1,1,1-

*Environmental Sustainability - Preparing for Tomorrow*

11, , and 11 (total 8 records).

**232**

trichloroethane (1,1,1-TCE) 7.7, n.o., 40, 23; 1,2-dichloropropane (1,2-DCP) 4900, 12, n.o., 44; 1,1-dichloroethene (1,1-DCEe) 51, 3.3, 34, 140; vinyl chloride 1700, 809, n.o., 1980; chlorobenzene 416, 71, 92, 100; cumene (*i*-propylbenzene) 194, 84, 35, 75; phenol 43, 348, 37, and 103; *o*-cresol (2-methylphenol) 1620, 99, n.o., 99; furan 27, 29, 130, 12; tetrahydrofuran (THF) 598, 372, n.o., 2830; thiophene 781, 578, 773, 550; acetic acid 7000, 12, 12, 650; dimethyl sulfide (DMS) 6650, 2230, n.o., 6780; dimethyl disulfide (DMDS) 518, 36, n.o., 97; formaldehyde 5.7, n.o., n.o., and 3.1. Pyridine was observed only in Radlin, in very constant amounts, 10–11 ppm. Although certified (as in the case of other compounds in the calibration library), the maximum contents of germanium tetrachloride, GeCl4, i.e., 3130, 209, 333, and 2098 should be treated with care due to possible coincidence as yet unresolvable by the Calcmet software. Geometric means of the concentration values (Pszów, Rybnik-Rymer, Radlin, Rydułtowy, whole series) are: H2O 31, 12, 3.0, 21, and 19 (*n*total = 46); CO2 31, 4.0, 0.22, 11, and 7.0 (*n*total = 50) [vol.%]; CO 84, 186, 9.6, 81, and 81 (*n*total = 41); NO 87, 15, 14, 66, and 42 (*n*total = 24); NO2 334, 38, 14, 42, and 41 (*n*total = 26); N2O -, 0.10, 0.66, 4.3, and 0.83 (*n*total = 17); NH3 287, 22, 3.4, 59, and 88 (*n*total = 18); SO2 110, 18, 17, 48, and 56 (*n*total = 31); HCl 7.4, 4.2, 0.56, 3.0, and 3.8 (*n*total = 46); CCl4 3.2, 0.18, 0.91, 2.5, and 1.6 (*n*total = 51); HF 4.0, 2.2, , 3.3, and 3.4 (*n*total = 9); SiF4 16, 114, 94, 182, and 65 (*n*total = 29); AsH3 1.1, 0.19, 0.17, 1.0, and 0.58 (*n*total = 26); CH4 1945, 500, 23, 537, and 457 (*n*total = 47); ethane 46, 114, 15, 75, and 59 (*n*total = 37); propane 148, 70, 16, 27, and 46 (*n*total = 27); hexane 160, 25, , 15, and 38 (*n*total = 26); ethene 7.9, 7.3, 11, 8.3, and 8.2 (*n*total = 28); DCM 230, 119, 160, 295, and 214 (*n*total = 45); 1,1-DCE 235, 190, 98, 99, and 139 (*n*total = 32); 1,2-DCE 153, 28, 7.4, , and 91 (*n*total = 9); 1,1,1-TCE 5.4, , 40, 9.5, and 7.7 (*n*total = 19); 1,2-DCP 1038, 5.7, , 20, and 166 (*n*total = 9); 1,1-DCEe 19, 2.6, 31, 25, and 20 (*n*total = 35); vinyl chloride 329, 38, , 394, and 289 (*n*total = 32); chlorobenzene 24, 36, 92, 32, and 32 (*n*total = 12); cumene 28, 30, 35, 15, and 22 (*n*total = 38); phenol 14, 36, 3.8, 32, and 19 (*n*total = 32); *o*-cresol 115, 21, , 99, and 73 (*n*total = 15); furan 11, 9.8, 72, 12, and 31 (*n*total = 18); THF 126, 372, , 643, and 195 (*n*total = 10); thiophene 251, 200, 90, 156, and 186 (*n*total = 40); formaldehyde 3.5, , , 0.54, and 0.82 (*n*total = 8); acetic acid 189, 6.6, 8.1, 83, and 54 (*n*total = 22); DMS 517, 433, , 921, and 533 (*n*total = 16); DMDS 68, 11, , 31, and 41 (*n*total = 35); and pyridine -, ,

GC results were also published in the paper, with confirmed occurrence of carbonyl sulfide, COS, carbon disulfide, CS2, freons (CCl3F, CCl2F2, CHClF2), *i*butane, *n*-butane, *i*-pentane, *n*-pentane, *n*-hexane, *n*-heptane, *n*-octane, *n*-nonane, *n*-decane, propene, 1-butene, *i*-butene, *trans*- and *cis*-2-butene, *trans*- and *cis*-2 pentene, ethyne, 1,3-butadiene, isoprene (2-methyl-1,3,-butadiene), 2,3-

dimethylbutane; 2- and 3-methylpentanes; benzene, toluene, *m*/*p*- and *o*-xylenes, styrene, ethylbenzene, *n*- and *i*-propylbenzene; 2-, 3,- and 4- (or *m*-, *p*- and o-) ethyltoluene; 1,2,3-, 1,2,4-, and 1,3,5-trimethylbenzenes; and α- and β-pinene. As shown in the paper, the GC results may be quite unreliable due to their non-*in situ* character and possible intra-gas and gas-steel interactions, and are thus not resumed here. In turn, we have later used a second and third mode of the FTIR spectra reading. The first one is an external library search, where the spectra are read and calculated using libraries containing other compound sets, thus reporting semiquantitative results with fit factor (r2 , in %), as described in Kruszewski et al. [12]. Any misfits are due to recording the standards in different conditions than in the DX-4000 calibration library case. Applying this method allowed to detect additional compounds for the previously listed 4 BCWH sites [in ppm, with results for fit ≥90%, 75–90%, 50–75%, and < 50%, and whole-data maximums underlined]: acetylene, C2H2 (up to 0.81; up to 27; up to 38; up to 288), *n*-butane (; ; 7.1; 1.5), *i*-butane (; ; 9.7; 0.25), propene (; ; up to 101; up to 30), *n*-pentane (; ; 4.0; 1.9), *i*-pentane (; ; 11; 0.91), heptane (; ; up to 2.1; ), octane (; ; up to 2.3; ), nonane (; ; up to 2.1; ), decane (; ; up to 2.0; ), undecane (; ; up to 2.0; ), 1,3-butadiene (3.2; ; up to 144; up to 169), cyclohexane (; ; up to 2.7; ), α-pinene (; ; up to 4.0; up to 1.1), limonene (C10H16; ; ; up to 4.9; 2.7), 3-carene (C10H16; 512; up to 2.2), benzene (8.8; up to 5.1; up to 52; up to 5700), toluene (; ; up to 74; up to 18), styrene (; 88; 0.76; up to 154), *m*-xylene (; ; 19; up to 51), *p*-xylene (; ; 16; up to 23), ethylbenzene (; ; ; up to 8.4), 1,3,5- TMB (; ; up to 729; up to 32), 1,2,4-TMB (; ; up to 1610; up to 27), 1,2,3-TMB (; ; up to 1360; up to 23), tetrachloroethene (; up to 4.3; up to 28; up to 27), methanol (11; 5.4; up to 18; up to 75), ethanol (16; 5.4; up to 38; up to 126), *i*propanol (isopropanol; ; ; ; up to 16), *i*-butanol (isobutanol; ; ; ; 5.4), *n*propanol (; ; 982; ), methanethiol (methylmercaptan), CH3SH (; ; ; up to 55), ethanethiol (ethylmercaptan), C2H5SH (; ; 2500; up to 14), HCN (up to 8.4; up to 16; up to 88; up to 65), acrylonitrile (prop-2-enenitrile, CH2 = CHCN; ; 6.0; up to 63; up to 82), isocyanic acid (; ; ; up to 717), formic acid, HCOOH (3.0; 8.7; up to 29; up to 48), trimethylamine, (C2H5)3N (; ; ; up to 1.5), acetaldehyde (up to 45; up to 97; up to 1810; up to 6270), propionaldehyde (propanal), (C2H5)CHO (; ; ; up to 24), 2-ethylhexylaldehyde (C4H9CH(C2H5)CHO; ; ; up to 342; ), acrolein (propenal, CH2 = CHCHO; ; 1.6; up to 57; up to 25), acetone (propan-2-one) (; ; ; up to 98), methyl ethyl ketone (MEK, or butan-2-one), CH3C(O)C2H5 (; ; ; up to 28), methyl isobutyl ketone (MIBK, or 4 methylpentan-2-on), (CH3)2C2H3C(O)CH3 (; ; ; up to 2.6), diethylether (ethoxyethane, (C2H5)2O; ; ; 1.7; up to 24), MTBE (; ; ; up to 9.4), 2 ethoxyethanol, (C2H5)O(CH2)O(C2H5) (; ; up to 47; up to 32), 2-ethoxyethyl acetate (; ; ; up to 19), butyl acetate (; ; ; up to 15), 2-(2-butoxyethoxy) ethyl acetate (; ; ; up to 13), methyl metacrylate (methyl 2-methylprop-2 enoate; ; ; ; up to 10), PH3 (phosphine; ; up to 43; up to 144; up to 152), COS (up to 0.88; up to 6.1; up to 0.40; ), and last but not least SF6 (; ; up to 1.6; up to 1.5). The last compound is environmentally very important, as it is said – by the Intergovernmental Panel on Climate Change – to be the most potent greenhouse gas [25]. The measured BCWH emanation concentrations are also much higher (over 170000 times) than the highest ones measured at Mauna Loa fumaroles [26]. Calculated geometric means (whole series; with values for fit ≥50% in the parentheses): 13 (2.3) for acetylene (*n* = 14 (31)), 25 (51) for propene (*n* = 9 (3)), 17 (29) for 1,3-butadiene (*n* = 15 (5)), 0.76 for α-pinene (*n* = 6), 3.5 for limonene (*n* = 3), 6.2 for 3-carene (*n* = 4), 55 (9.7) for benzene (*n* = 34 (14)), 7.4 (21) for toluene (*n* = 11 (3)), 9.6 for styrene (*n* = 9), 9.9 (10) for *m*-xylene (*n* = 11 (8)), 13 for *p*-xylene (*n* = 7), 13 (13) for 1,3,5-TMB (*n* = 11 (8)), 11 for 1,2,4-TMB (*n* = 10), 4.5 for 1,2,3- TMB (*n* = 6), 15 (5.5) for methanol (*n* = 24 (4)), 32 (8.6) for ethanol (*n* = 26 (7)), 6.9 for *i*-propanol (*n* = 7), 23 for ethanethiol (*n* = 4), 4.2 (1.4) for tetrachloroethene (*n* = 31 (9)), 7.2 (5.9) for HCN (*n* = 47 (33)), 293 for isocyanic acid (*n* = 18), 1.2 for trimethylamine (*n* = 3), 47 (47) for acrylonitrile (*n* = 12 (9)), 15 (12) for formic acid (*n* = 35 (7)), 62 (28) for acetaldehyde (*n* = 50 (45)), 9.4 for propionaldehyde

(*n* = 4), 37 for 2-ethylhexylaldehyde (*n* = 3), 23 (28) for acrolein (*n* = 13 (9)), 21 for acetone (*n* = 22), 5.2 for diethylether (*n* = 10), 6.8 for 2-ethoxyethanol (*n* = 10), 7.7 for 2-ethoxyethyl acetate (*n* = 20), 4.8 for butyl acetate (*n* = 8), 5.1 for methyl metacrylate (*n* = 9), 12 for MEK (*n* = 8), 2.0 for MIBK (*n* = 5), 2.7 for MTBE (*n* = 4), 0.37 (0.41) for COS (*n* = 16 (13)), 72 (40) for PH3 (*n* = 28 (10)), and 1.1 for SF6 (*n* = 10). As such, acetaldehyde, HCN, PH3, tetrachloroethene, ethanol, benzene, COS, methanol, acetylene, and 1,3-butadiene, isocyanic acid, acrolein, and likely acetone and 2-ethoxyethyl acetate seem to be the most frequent admixing gases in the BCWH exhausts studied.

The third operation mode is qualitative analysis of residual spectra, as thoroughly described in both my previous papers. This method allowed to list proposals of additional, very interesting, admixing gases, many of which were likely first documented in the nature. They include neutral hydroxides of Ca, Mg, Al, Fe(II), Fe (III), Zn, Cu; nitrosyls and carbonyls of Ti, V, Mn, Fe, Ag, Mo, Fe, Cu; hydrides of Al, Cu, Zn, Ge, Mo, Sb, and Hg; nitriles, azo and related compounds (azacyclopropenylidene, dicyanoacetylene, cyanogen isocyanate, cyanogen *N*-oxide, diazomethyl radical, hydrogen isocyanide, isocyanic acid, *m*-hydroxybenzonitrile, phenylnitrene radical; 2,4,6-trinitrene-1,3,5-triazine); amines (methyl(nitrosomethyl)amine); hypobromous and hydroiodic acids; hydrocarbons and halocarbons (cyclohexene, dibenz[*a*,*h*]anthracene, difluorovinylidene, hexachlorobenzene, hexachloroethane, 5 methyl-1,3-didehydrobenzene, pentacene, phenanthrene, triphenylene); nitrosyl chloride and iodide, phosgene; organoboron compounds (fluoroisocyanatoborane) and compounds like CBrO and B2O2; organosulfurs (thiirene, thioacetaldehyde, thioxoethenylidyne radical), organophosphorus compounds (methylphosphine), and organosilicons (difluorosilane, disinale, silanenitrile, tribromosilane), organoiodine compounds (iodosomethane – an I3+-bearing compounds; iodocyanoacetylene), HAlCl2, ClO2 \* , and dimeric NO, to mention some. Due to multiple coincidence possible these results should, however, be treated with care.

### **4. New** *in situ* **FTIR gas analysis results of the USCB heaps**

Results presentation within this chapter has its main goal in enlarging the span of the knowledge on the concentration range of various (major and minor) components of the BCWH combustion gases, both by pFTIR and GC methods. **Table 1** shows data from Czerwionka-Leszczyny (18, that is, 10 vents / vent zones from zone CLD and 8 from the CL one). **Table 2** juxtaposes data for 10 additional, differently mineralized vents from the Radlin heap (RD), with that from a BCWH in Bytom (BTM, 7 vents / vent zones). **Table 3**, in turn, juxtaposed data for vents in a BCWH in Świętochłowice (SWC, 11 vents / vent zones), "Starzykowiec" heap in the Chwałowice part of Rybnik (RCH, 1 vent, surface and deep part), and "Ruda" heap in Zabrze-Biskupice (ZBB, 5 vents / vent zones). In total, data for additional 53 vents is reported. As in the case of the data presented in Kruszewski et al. [6, 12], gases were probed at the surface and from deeper parts of the vents, whenever possible. Temperatures were measured using an IR pyrometer.

Following are values describing maximum and geometric-mean concentrations of gaseous species as detected within fumarolic vents of the CLD, CL, RD, BTM, SWC, and ZBB sites (whole-series-maximums are underlined): H2O, 18.12, 14.74; 7.30, 2.83; 27.14, 23.04; 11.15, 9.83; 6.42, 4.68; 25.63, 23.19; CO2, 2.85, 2.29; 27.00, 0.20; 29.89, 20.85; 8.12, 6.05; 38.41, 33.89 [vol.%]; CO, 135, 110; 163, 9.4; 2430, 1002; 3590, 2675; 1090, 303; 26700, 3257; NO, 112, 96; 10, 6.4; 7.3, 7.3; , ; 19, 15; , ; NO2, 44, 22; 368, 155; 2.0, 2.0; 1430, 1430; , ; 66, 45; N2O, 3.5, 2.3; 0.06, 0.02; 4.4, 4.4; 2.8, 2.8; 1.3, 1.3; , ; NH3, 21, 7.7; 30, 2.5; 19, 7.1; 65, 55; 4.1, 2.4; 8.3,

**vent 1**

**235**

T [oC]

H

O2 2

CO2

CO

N O

2

NO

NO2 NH3

SO2 HCl

CCl4

HF

SiF4 AsH3

CH4 ethane

propane

hexane

 1.8

 0.20

 0.31

 0.35

 2.6

 4.6

 2.3

 7.0

 4.6

 11

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

**152**

17

 6.9

 3.8

 4.4

 4.4

 34

 42

 36

 bdl

 40

 37

 bdl

 4.2

 3.1

 13

 11

 8.2

 bdl

**729**

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 30

 bdl

26

 31

 31

 31

**244**

 **259**

 **262**

 **251**

 **253**

 **248**

4.5

 4.8

 6.8

 4.6 0.51

 4.8

**811**

 **2950**

bdl

 0.08

 0.17

 0.15

 0.03

 bdl

 bdl *aliphatic and aromatic* 

*hydrocarbons*

 *and their derivatives*, *ppm*

 bdl

 bdl

 bdl

 bdl

 bdl

 0.16

 bdl

 bdl

 bdl

 0.20

**1.7**

bdl

 0.06

 0.21

 0.16

 3.7

 5.3

 3.8

 3.4

 6.3

 4.6

 2.2

 1.9

 1.9

 2.1

 1.1

 2.1

 20

 31

 bdl

 bdl

 bdl

 bdl

 bdl

 0.62

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 0.03

bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 6.6

 0.04

 bdl

 0.24

 0.57

 11

 10

 10

 8.7

 7.6

 6.6

 1.5

 0.76

 0.08

 0.58 0.01

 0.63

 6.5

 5.8

4.2

 bdl

 bdl

 bdl

 bdl

 87

 bdl

 bdl

 20

 120

 bdl

 bdl

 bdl

 1.9

 bdl

 2.4

**119**

 **671**

4.4

 3.9

 3.6

 3.7

 10

 15

 21

 10

 11

 9.4

 bdl

 1.0

 0.23

 1.4

 bdl

 1.4

 18

 30

bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 11

 44

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

**368**

65

 64

**107**

 **112**

 **112**

bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 6.9

 9.9

 bdl

 9.7

 1.6

 10

 bdl

 bdl

 2.8

 3.4

 3.5

 3.5

 bdl

 bdl

 bdl

 bdl

 bdl

 0.57

 0.02

 0.04

 0.06

 0.01

 bdl

 0.02

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

**1353**

**101**

 **101**

 **132**

94

**103**

6.4

 3.1

 bdl

 0.98

 bdl

 1.5

 145

 163

1.96

 2.32 *inorganics, ppm*

 2.34

 2.40

 1.90

 2.26

 2.08

 2.39

 2.54

 2.85

 0.03

 0.03

 0.03

 0.03

 bdl

 0.03

 18.00

 27.00

*Fossil Fuel Fires: A Forgotten Factor of Air Quality DOI: http://dx.doi.org/10.5772/intechopen.96294*

9.77

 12.21

 12.22

 12.27

 16.43

 17.36

 16.88

 17.62

 17.65

 18.12

 2.68

 2.65

 2.57

 2.58 0.75

 2.62

 6.10

 7.30

 40

 45

 45

 45

 25

 35

 35

 35

 35

 60

**pFTIR**

*inorganics, vol.%*

 90

 90

 82

 82

 50

 82

 30

 45

**CLD1**

 **CLD1o**

 **CLD2**

 **CLD3**

 **CLD5**

 **CLD5S**

 **CLD5o**

 **CLD6o**

 **CLD6o2**

 **CLD7**

 **CLdA**

 **CLdAr**

 **CLdU**

 **CLd CL1 CLdo**

 **CL2a**

 **CL2aA**


## *Fossil Fuel Fires: A Forgotten Factor of Air Quality DOI: http://dx.doi.org/10.5772/intechopen.96294*

(

(

acetone (

dibenz[ *a* ,

HAlCl

a BCWH in

the Chwa

 , ; NO

**234**

metacrylate (

*n* = 4), 37 for 2-ethylhexylaldehyde (

for 2-ethoxyethyl acetate (

the BCWH exhausts studied.

0.37 (0.41) for COS (

*n* = 22), 5.2 for diethylether (

*Environmental Sustainability - Preparing for Tomorrow*

*n* = 9), 12 for MEK (

*n* = 10). As such, acetaldehyde, HCN, PH

radical, hydrogen isocyanide, isocyanic acid,

and compounds like CBrO and B

compounds (iodosomethane

Świ ętoch

0.02; 4.4, 4.4; 2.8, 2.8; 1.3, 1.3;

2, ClO 2 \* *n* = 3), 23 (28) for acrolein (

3 (

*n* = 20), 4.8 for butyl acetate (

COS, methanol, acetylene, and 1,3-butadiene, isocyanic acid, acrolein, and likely acetone and 2-ethoxyethyl acetate seem to be the most frequent admixing gases in

described in both my previous papers. This method allowed to list proposals of additional, very interesting, admixing gases, many of which were likely first

radical; 2,4,6-trinitrene-1,3,5-triazine); amines (methyl(nitrosomethyl)amine); hypobromous and hydroiodic acids; hydrocarbons and halocarbons (cyclohexene,

methyl-1,3-didehydrobenzene, pentacene, phenanthrene, triphenylene); nitrosyl chloride and iodide, phosgene; organoboron compounds (fluoroisocyanatoborane)

thioxoethenylidyne radical), organophosphorus compounds (methylphosphine), and organosilicons (difluorosilane, disinale, silanenitrile, tribromosilane), organoiodine

Results presentation within this chapter has its main goal in enlarging the span of the knowledge on the concentration range of various (major and minor) components of the BCWH combustion gases, both by pFTIR and GC methods. **Table 1** shows data from Czerwionka-Leszczyny (18, that is, 10 vents / vent zones from zone CLD and 8 from the CL one). **Table 2** juxtaposes data for 10 additional, differently mineralized vents from the Radlin heap (RD), with that from a BCWH in Bytom (BTM, 7 vents / vent zones). **Table 3**, in turn, juxtaposed data for vents in

łowice (SWC, 11 vents / vent zones),

łowice part of Rybnik (RCH, 1 vent, surface and deep part), and

Following are values describing maximum and geometric-mean concentrations of gaseous species as detected within fumarolic vents of the CLD, CL, RD, BTM,

> ,

; 66, 45; N

3, 21, 7.7; 30, 2.5; 19, 7.1; 65, 55; 4.1, 2.4; 8.3,

0.20; 29.89, 20.85; 8.12, 6.05; 38.41, 33.89 [vol.%]; CO, 135, 110; 163, 9.4; 2430,

heap in Zabrze-Biskupice (ZBB, 5 vents / vent zones). In total, data for additional 53 vents is reported. As in the case of the data presented in Kruszewski et al. [6, 12], gases were probed at the surface and from deeper parts of the vents, whenever

2 O

**4. New** *in situ* **FTIR gas analysis results of the USCB heaps**

possible. Temperatures were measured using an IR pyrometer.

SWC, and ZBB sites (whole-series-maximums are underlined): H

1002; 3590, 2675; 1090, 303; 26700, 3257; NO, 112, 96; 10, 6.4; 7.3, 7.3;

7.30, 2.83; 27.14, 23.04; 11.15, 9.83; 6.42, 4.68; 25.63, 23.19; CO

 , ; NH

2, 44, 22; 368, 155; 2.0, 2.0; 1430, 1430;

possible these results should, however, be treated with care.

*h*]anthracene, difluorovinylidene, hexachlorobenzene, hexachloroethane, 5-

, and dimeric NO, to mention some. Due to multiple coincidence

*n* = 16 (13)), 72 (40) for PH

*n* = 8), 2.0 for MIBK (

The third operation mode is qualitative analysis of residual spectra, as thoroughly

documented in the nature. They include neutral hydroxides of Ca, Mg, Al, Fe(II), Fe (III), Zn, Cu; nitrosyls and carbonyls of Ti, V, Mn, Fe, Ag, Mo, Fe, Cu; hydrides of Al, Cu, Zn, Ge, Mo, Sb, and Hg; nitriles, azo and related compounds (azacyclopropenylidene, dicyanoacetylene, cyanogen isocyanate, cyanogen *N*-oxide, diazomethyl

*n* = 10), 6.8 for 2-ethoxyethanol (

*n* = 13 (9)), 21 for

*n* = 8), 5.1 for methyl

*n* = 5), 2.7 for MTBE (

*n* = 28 (10)), and 1.1 for SF

3, tetrachloroethene, ethanol, benzene,

*m*-hydroxybenzonitrile, phenylnitrene

"Starzykowiec

" heap in

"Ruda "

; 19, 15;

2O, 18.12, 14.74;

2, 2.85, 2.29; 27.00,

 ,

2O, 3.5, 2.3; 0.06,

2; organosulfurs (thiirene, thioacetaldehyde,

– an I3+-bearing compounds; iodocyanoacetylene),

*n* = 10), 7.7

*n* = 4),

6


**GC** –

**vent**

**237**

CH3Cl

ethyne

propene

*i*-butane

*n*-butane

1-butene

*i*-butene

*t*

2-bu

*c*-2-bu

**vent**

*i*-pentane

*n*-pentane

*t*-2-pte

*c*-2-pte

*n*-heptane

*n*-octane

*n*-nonane

*n*-decane

2,3-DMBu

2-MPT

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 0.0003

 0.001

 **CLD1**

 **CLD1o**

 **CLD2**

 **CLD3**

0.01

0.01

0.002

0.001

0.003

0.002

0.0003

0.0001

0.01

0.01

 0.41

 0.07

 0.16

 0.25

 0.36

 0.44

 0.08

 0.20

 1.1

 0.92

 **CLD5 CLD5S**

 **CLD5o**

 **CLD6o**

1.8 2.3 0.57 0.23 0.84 0.65 0.40 0.20 0.13 0.76

0.75

0.16

0.003

0.03

0.10

0.34

0.07

0.19

1.5

1.8

 **CLD6o2**

 **CLD7 CLdA CLdAr**

 **CLdU CLd**

 **CL1 CLdo CL2a CL2aA**

0.06

0.06

0.01

0.004 0.003

0.02

0.01

0.01

0.001 0.002

0.003

0.02

 0.11

 3.0

 0.82

 0.02

 0.58

 0.14

 0.03

 0.04

 0.01

 0.22

 0.04

 0.04

 0.64

 0.32

 0.07

 1.7

 0.68

 0.09

 0.04

 0.01

 0.36

 0.18

 0.35

 6.0

 1.9

 0.35

 6.5

 1.7

 0.00003

 0.00004

 0.0001

 0.0001

 0.001

 0.0003

 0.0002

 0.001

 0.002

 **CLD1**

 **CLD1o**

 **CLD2**

 **CLD3**4

0.001

0.001

bdl

0.002

0.002

0.001

0.002

0.001

0.0005

 0.29

 0.52

 0.41

 0.14

 2.4

 1.6

 1.7

 0.001

 0.003

**CLD5 CLD5S**

 **CLD5o**

 **CLD6o**

0.002 0.001

5.2 3.2 5.4 0.40 0.32

1.4 0.80

0.23

0.50

0.52

0.13

3.6

3.5

1.4

0.01

0.005

 **CLD6o2**

 **CLD7 CLdA CLdAr**

 **CLdU CLd**

 **CL1 CLdo CL2a CL2aA**

0.002

0.003

0.09

0.08

0.15

0.02

0.03

0.02

0.01

 0.02

 0.17

 0.06

 0.04

 0.59

 0.24

 0.04

 1.3

 0.42

 0.03

 0.08

 0.03

 1.1

 12

 3.9

 0.69

 8.3

 2.3

*Fossil Fuel Fires: A Forgotten Factor of Air Quality DOI: http://dx.doi.org/10.5772/intechopen.96294*

> 0.51

 0.36

 0.09

 0.01

 0.01 0.0002

 0.08

 0.03

 0.01

additional compounds, *ppm*


## *Fossil Fuel Fires: A Forgotten Factor of Air Quality DOI: http://dx.doi.org/10.5772/intechopen.96294*

**vent 1**

**236**

ethene

DCM

1,1-DCE

1,2-DCE

**vent**

1,1,1-TCE

1,2-DCP

1,1-DCEe

ClB

cumene

phenol

*o*-cresole

furan

THF

py tph

fm

DMS

DMDS)

12

 23

 32

 28

**99**

 **104**

40

 7.0

 85

 5.6

 3.5

 37

 31

 36

 17

 36

 bdl

 bdl

 bdl

 13

 7.7

 11

 62

 6.9

 27

 33

 31

 51

 bdl

 0.15

 bdl

 bdl

 bdl

 bdl

**893**

 **165**

 0.11

 bdl

 bdl

 bdl

 12

 7.0

 6.0

 5.3

 5.3

 5.7

 0.58

 1.2

 0.47

 0.42 0.45

 0.42

 13

 13

 bdl

 bdl

 bdl

 bdl

**192**

 **137**

 **191** *other organic compounds*, *ppm*

bdl

**127**

 **103**

bdl

 bdl

 bdl

 bdl

 8.3

 bdl

 bdl

**173**

bdl

 bdl

 bdl

 bdl

 bdl

 7.1

 bdl

 bdl

 bdl

 bdl

 0.27

 2.3

 6.3

 12

 23

 12

 86

 bdl

 0.29

 bdl

 1.3

 0.18

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

**177**

 bdl

 0.14

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 0.29

 bdl

 0.41

 0.37

 19

 46

 17

 20 *heterocyclic organic compounds*, *ppm*

 23

 24

 1.9

 2.2

 0.28

 7.1 0.81

 6.9

 66

 10

 2.4

 4.4

 4.2

 4.0

 29

 bdl

 29

 28

 17

 17

 4.6

 3.2

 7.0

 bdl

 2.9

 bdl

 bdl

 bdl

 4.4

 6.3

 6.4

 5.5

 29

 30

 31

 29

 34

 31

 6.1

 1.3

 7.6

 1.9

 2.4

 1.7

**399**

bdl

 bdl

 bdl

 bdl

 bdl

 20

 bdl

 18

 39

 bdl

 bdl

 15

 14

 22

 6.0

 6.0

 6.3

 bdl

**186**

 4.3

 5.3

 4.4

 4.8

 57

 77

 54

 63

 43

 68

 35

 45

 49

 48

 25

 57

**226**

 **347**

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 31

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 56

 bdl

 bdl

 bdl

 bdl

 bdl

**99**

bdl

 bdl

 bdl

 bdl

 21

 bdl

 bdl

 bdl

 6.4

 bdl

 6.5

**417**

bdl

*Environmental Sustainability - Preparing for Tomorrow*

 **CLD1**

 **CLD1o**

 **CLD2**

 **CLD3**

 **CLD5**

 **CLD5S**

 **CLD5o**

 **CLD6o**

 **CLD6o2**

 **CLD7**

 **CLdA**

 **CLdAr**

 **CLdU**

 **CLd CL1 CLdo**

 **CL2a**

 **CL2aA**

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 77

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 7.2

 bdl

 bdl

 bdl

 5.1

 bdl

 7.4

 bdl

 7.2

 17

 12

 17

 10

 16

 15

 73

**104**

71

 141

 57

 20

 52

 65

 56

 50

 18

 51

**368**

 **159**

 bdl

 bdl

 bdl

 bdl

 bdl

 1.3

 bdl

 bdl

 3.7

 6.6

 2.2

 bdl

 1.3

 bdl

 1.9

 bdl

 37

 79

**CLD1**

 **CLD1o**

 **CLD2**

 **CLD3**

 **CLD5**

 **CLD5S**

 **CLD5o**

 **CLD6o**

 **CLD6o2**

 **CLD7**

 **CLdA**

 **CLdAr**

 **CLdU**

 **CLd CL1 CLdo**

 **CL2a**

 **CL2aA**


*formaldehyde, DMS – dimethyl sulfide, DMDS – dimethyl disulfide;* t*(*c*)-2-bu –* trans*(*cis*)-2-butene,* c*(*t*)-2-pte –* cis*(*trans*)-2-pentene, DMBu – dimethylbutane, MPT – methylpentane, cpt – cyclopentane, EtB – ethylbenzene, X – xylene, PrB – propylbenzene, EtT – ethyltoluene,TMB – trimethylbenzene; vinyl chloride, acetic acid, isoprene, and 1,3-butadiene were analyzed but were below their detection limits.*

*3Notable (>100 ppm) enrichment given in4GC data for a nearby vent.*

 *bold.*

#### **Table 1.**

**vent1**

**239**

T [oC]

H

O2 2

CO2

CO N O

2

NO

NO2 NH3

SO2 HCl

CCl4

HF

SiF4 AsH3 methane

ethane

propane

hexane

ethene

 bdl

 0.71

 12

 5.4

 9.3

 7.6

 12

 12

 3.1

 6.9

 4.7

 16

 17

 39

 84

 78

 35

 71

**139**

70

 53

 90

 67

 71

 53

 64

 76

 88

**148**

 **160**

 **309**

 **608**

 **543**

 **138**

**387**

 **601**

 **202**

bdl

**291**

 **230**

 **213**

bdl

**195**

 **249**

bdl

 bdl

 bdl

 bdl

**694**

 **242**

bdl

 bdl

**142**

bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

**281**

bdl

 bdl

**3190**

 **3470**

 **1120**

 **713**

 **1120**

 **1160**

 **1140**

 **500**

 **1120**

 **1150**

 **285**

 **437**

 **421**

 **359**

 **808**

 **819**

 **554**

bdl

**1.3**

0.93

 0.49

**1.2**

 **1.4** *aliphatic and aromatic* 

*hydrocarbons*

 *and their derivatives*, *ppm*

0.56

**1.7**

bdl

 0.11

 0.81

**2.9**

 **1.3**

 **2.0**

0.79

**2.8**

 **3.4**

15

 13

 21

 16

 15

 15

 18

 17

 14

 13

 1.7

 1.8

 1.7

 0.95

 bdl

 3.2

 bdl

 0.12

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 0.59

 0.07

 1.1

 bdl

 bdl

 bdl

6.3

 5.1

 10

 4.4

 6.8

 6.9

 3.2

 7.4

 11

 7.8

 bdl

 bdl

 bdl

 bdl

 1.1

 bdl

 bdl

 4.5

 3.1

 6.1

 2.9

 2.5

 2.6

 6.2

 bdl

 5.0

 2.3

 2.7

 3.3

 3.6

 5.4

 19

 15

 6.3

**388**

 **311**

bdl

 57

 bdl

**193**

bdl

 79

 bdl

 bdl

 86

**139**

 **147**

 **139**

 **532**

 **378**

 **281**

9.2

 9.2

 5.5

 6.9

 12

 19

 5.0

 1.8

 3.1

 16

 42

 60

 60

 61

 62

 65

 41

bdl

 2.0

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

**1430**

bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 7.3

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 4.4

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 2.8

**1580**

 **2430**

 **923**

 **502**

 **1110**

 **813**

 **832**

 **673**

 **1030**

 **1100**

 **1730**

 **2830**

 **3090**

 **2640**

 **3090**

 **3590**

 **2210**

25.00

 29.89

 20.21

 13.94

 26.16

 21.32

 21.24

 11.96

 21.14 *inorganics, ppm*

 24.64

 4.08

 5.43

 5.52

 5.25

 7.58

 8.12

 7.49

*Fossil Fuel Fires: A Forgotten Factor of Air Quality DOI: http://dx.doi.org/10.5772/intechopen.96294*

19.99

 24.62

 26.02

 18.26

 27.14

 22.25

 26.61

 16.94

 24.80

 26.65

 6.92

 9.94

 10.41

 10.67

 11.15

 11.02

 9.43

 60

 90

 133

 187

 77

 107

 76

 76 **pFTIR**

*main components,*

 *vol. %*

 76

 76

 115

 144

 73

 150

 79

 115

 60

**RD07 RD07A**

 **RD08N**

 **RD08NA**

 **RD08kr**

 **RD08krA**

 **RD08o**

 **RD11L RD11U**

 **RD11o BTM1 BTM1A**

 **BTM1o**

 **BTM1o2**

 **BTM1o3**

 **BTM1o4**

 **BTM2**

*Results of the pFTIR and GC gas analyses of BCWH in Czerwionka-Leszczyny.*


## *Fossil Fuel Fires: A Forgotten Factor of Air Quality DOI: http://dx.doi.org/10.5772/intechopen.96294*

**vent**

**238**

3-MPT

cpt benzene

toluene

EtB

*m/p*-X

*o*-X

styrene

*i*-PrB *n*-PrB

*m*-EtT

*p*-EtT

*o*-EtT

1,3,5-TMB

1,2,4-TMB

1,2,3-TMB

*Values in parentheses* *1"A" – samples taken from the depth of 0.8–1 m; "a" and "o" - nearby vents; "r" – repeated analysis; "S" –*

*2DCM –* *formaldehyde,*

*cyclopentane,*

*detection limits.* *3Notable (>100 ppm) enrichment given in bold.*

*4GC data for a nearby vent.*

**Table 1.** *Results of the pFTIR and GC gas analyses of BCWH in* 

*Czerwionka-Leszczyny.*

 *EtB –*

*ethylbenzene,*

 *X – xylene, PrB –*

*propylbenzene,*

 *EtT –*

*ethyltoluene,TMB*

 *–*

 *DMS – dimethyl sulfide, DMDS – dimethyl disulfide;* t*(*c*)-2-bu –*

*dichloromethane,*

 *DCE –*

*dichloroethane,*

 *DCEe –*

*dichloroethene,TCE*

 *–*

*trichloroethane,*

 *DCP –*

trans*(*cis*)-2-butene,*

*trimethylbenzene;*

 *vinyl chloride, acetic acid, isoprene, and* 

c*(*t*)-2-pte –*

 *denote overrun of the upper* 

 0.0001

 0.0001

 0.0001

 bdl

 bdl

 0.0001

 bdl

bdl

 0.001

 0.0002

 0.0003

 0.0001

 0.001

 0.0004

bdl

 0.0001

 **CLD1**

 **CLD1o**

 **CLD2**

 **CLD3** 0.005

0.001

0.002

0.02

0.003

0.01

0.003

0.0001

0.0002

0.0005

0.001

0.0005

0.0005

0.001

0.002

0.001

*measurement*

 *range.*

 0.10

 0.27

 0.14

 0.08

 0.07

 0.18

 0.06

 0.03

 bdl

 0.39

 1.3

 0.27

 2.0

 2.1

 0.19

 0.16

 **CLD5 CLD5S**

 **CLD5o**

 **CLD6o**

0.30 0.42

3.3 3.4 0.43

1.9 0.53 bdl 0.05 0.08 0.24 0.10 0.10 0.19 0.32 0.10

0.02 *sulfur-mineralized*

*dichloropropane,*

 *ClB –* cis*(*trans*)-2-pentene,*

 *DMBu –*

*chlorobenzene,THF*

 *–*

*dimethylbutane,*

 *MPT –*

*1,3-butadiene*

 *were analyzed but were below their*

*methylpentane,*

 *cpt –*

*tetrahydrofuran,*

 *py – pyridine, tph –*

*thiophene, fm –*

 *vent.*

0.05

0.07

0.02

0.02

0.06

0.02

0.03

bdl

0.03

0.19

0.01

0.01

0.06

0.26

0.30

 **CLD6o2**

 **CLD7 CLdA CLdAr**

 **CLdU CLd**

 **CL1 CLdo CL2a CL2aA**

0.01

0.01

0.05

0.02

0.01

0.02

0.01

bdl

0.001 0.001 0.001 0.002

0.004

0.001 0.003 0.003 0.002 0.003 0.005

0.01

0.004 0.003

 0.06

 0.05

 0.01

 0.04

 0.03

 0.01

 0.005

 0.01

 0.01

 0.01

 0.01

 0.01

 0.01

 0.01

 0.02

 0.01

 0.06

 0.03

 bdl

 bdl

 bdl

 0.03

 0.02

 0.01

 0.09

 0.06

 0.22

*Environmental Sustainability - Preparing for Tomorrow*

 0.02

 0.12

 0.05

 0.11

 0.05

 0.02

 0.27

 1.1

 0.41

 0.05

 1.0

 0.30

 0.05

 1.3

 0.34


**vent**

**241**

ethyne

propene

*i*-butane

*n*-butane

1-butene

*i*-butene

*t*-2-bu

*c*-2-bu

*i*-pentane

**vent**

*n*-pentane

isoprene

1,3-budi

*t*-2-pte

*c*-2-pte

*n*-heptane

*n*-octane

*n*-nonane

*n*-decane

2,3-DMB

2-MPT

3-MPT

cpt

 0.70

 0.26

 0.64

 0.12

 0.003

 0.03

 0.05

 0.44

 0.05

 0.12

 bdl

 bdl

 3.3

 **RD07 RD07A**

 **RD08N**

1.1

0.002

bdl

0.01

0.003

0.18

0.05

0.46

0.02

0.04

0.22

0.10

0.25

 0.01

 0.0004

 0.003

 0.40

 0.27

 0.02

 0.001

 0.001

 0.22

 0.17

 0.01

 0.001

 0.02

 0.53

 0.43

 0.003

 0.0002

 0.004

 0.09

 0.08

 0.01

 0.0001

 0.0002

 0.02

 0.11

 0.02

 0.0003

 0.001

 0.08

 0.15

 0.03

 0.0007

 0.004

 0.18

 0.21

 0.03

 0.001

 0.01

 0.58

 0.41

 0.03

 0.0004

 0.002

 0.09

 0.03

 0.06

 0.001

 0.01

 0.21

 0.08

 0.02

 0.0002

 bdl

 bdl

 bdl

 0.03

 0.0003

 0.001

 0.02

 0.01

 0.07

 0.005

 0.06

 2.1

 1.2

1.7 0.13 0.03 0.81 0.39 0.93 0.57 0.44 0.60 0.08 0.33 0.11 0.22

 **RD08NA**

 **RD08kr**

 **RD08krA**

 **RD08o**

 **RD11L RD11U RD11o BTM1 BTM1A**

 2.0

 0.01

 0.01

 0.06

 0.01

 8.7

 3.3

 0.47

 0.01

 **RD07 RD07A**

 **RD08N**

0.01

0.91

1.7

3.6

0.02

0.08

0.06

0.03

0.77

 0.04

 0.004

 0.09

 1.2

 1.1

 0.12

 0.0005

 0.003

 0.47

 0.18

 0.16

 0.001

 0.01

 0.78

 0.24

 0.51

 0.002

 0.01

 0.98

 0.38

 0.13

 0.003

 0.005

 0.24

 0.13

 0.21

 0.01

 0.03

 4.6

 3.4

 0.08

 0.005

 0.13

 2.0

 2.6

 0.93

 0.01

 0.03

 3.8

 1.5

 0.001

 0.003

 0.003

 0.002

 0.04

 **RD08NA**

 **RD08kr**

 **RD08krA**

 **RD08o**

 **RD11L RD11U**

 **RD11o BTM1 BTM1A**

0.002

8.5 2.4 5.9 1.6 6.6 2.3 1.6 1.2

 **BTM1o**

 **BTM1o2**

 **BTM1o3**

 **BTM1o4**

 **BTM2**

0.91

0.003

bdl

0.01

0.003

0.11

0.05

0.10

0.01

0.06

0.28

0.17

0.20

 **BTM1o**

 **BTM1o2**

 **BTM1o3**

 **BTM1o4**

 **BTM2** 0.004

0.62

1.7

2.6

0.05

0.26

*Fossil Fuel Fires: A Forgotten Factor of Air Quality DOI: http://dx.doi.org/10.5772/intechopen.96294*

0.07

0.04

0.80


## *Fossil Fuel Fires: A Forgotten Factor of Air Quality DOI: http://dx.doi.org/10.5772/intechopen.96294*

**vent1**

**240**

DCM

1,1-DCE

1,2-DCE

**vent**

1,1,1-TCE

1,2-DCP 1,1-DCEe

ViCl

ClB

cumene

phenol

*o*-cresole

THF

tph

fm

acac

DMS **vent**

CH3Cl

COS

 7.4

 0.001

 **RD07 RD07A**

 **RD08N**

0.05

0.78

 2.6

 0.88

 0.16

 2.1

 0.43

 1.4

 0.03

 0.03

 0.02

 0.01

 **RD08NA**

 **RD08kr**

 **RD08krA**

 **RD08o**

 **RD11L RD11U**

 **RD11o BTM1 BTM1A**

0.10

1.3

 **BTM1o**

 **BTM1o2**

 **BTM1o3**

 **BTM1o4**

 **BTM2**

0.02

0.98

**131**

 **126**

47

**401**

bdl

 16

 70

**GC –**

**additional** 

**compounds***, ppm*

**255**

27

 15

**172**

 **219**

 **243**

 **1540**

 **1370**

 **1200**

bdl

 bdl

 9.1

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 2.2

 bdl

 35

 9.9

 50

 bdl

 bdl

 2.6

 1.4

 2.0

 2.0

 5.5

 1.4

 1.3

 1.6

 0.74

 0.77

 0.91

 1.2

**17**

 **17**

2.1

**164**

 **257**

 **337**

 **385**

 **363**

 **369**

 **344**

 **301** *other organic compounds*, *ppm*

 **556**

 **391**

63

 bdl

 bdl

 bdl

**689**

 **201**

 **388**

 43

**96**

bdl

 3.1

 bdl

 9.3

 8.7

 4.1

 6.1

 12

 bdl

 bdl

 bdl

**232**

bdl

 bdl

**293**

 37

 65

 25

 40

 34

 50

 26

 39 *heterocyclic organic compounds*, *ppm*

 30

 31

 27

 46

 48

 53

 81

 73

 76

 bdl

 15

 49

 bdl

 21

 1.6

 51

 bdl

 11

 17

 18

 39

 42

 47

 60

 67

 35

**94**

 **126**

 **119**

36

**101**

 **108**

 **123**

 **105**

 **114**

90

 38

 46

 50

**264**

 **117**

bdl

**107**

 bdl

 bdl

 bdl

 bdl

 11

 bdl

 74

 bdl

 77

 62

 62

 46

 61

**112**

73

**206**

bdl

**416**

 **96**

 **276**

 **187**

 **248**

 **283**

 **269**

bdl

**203**

 **278**

38

 29

 47

 63

**137**

 **205**

 **359**

 81

 30

**195**

 **101**

 **164**

 **123**

 **176**

 **155**

 **189**

 **162**

bdl

 11

 11

 bdl

 24

 28

 bdl

**124**

 **384**

75

 42

**264**

 **175**

 **224**

 **108**

 **251**

 **248**

bdl

 bdl

 39

 bdl

**568**

bdl

**519**

*Environmental Sustainability - Preparing for Tomorrow*

 29

 15

 21

 33

 29

 36

 bdl

 21

 bdl

 bdl

 bdl

 bdl

 1.0

 bdl

 59

 bdl

 20

 **RD07 RD07A**

 **RD08N**

 **RD08NA**

 **RD08kr**

 **RD08krA**

 **RD08o**

 **RD11L RD11U**

 **RD11o BTM1 BTM1A**

 39

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 **BTM1o**

 **BTM1o2**

 **BTM1o3**

 **BTM1o4**

 **BTM2**

 38

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 16

 bdl

 bdl

 bdl

 8.3

 18

**126**

29

**104**

25

**111**

 **94**

 **102**

34

 11

 68

 74

 84

 bdl

 bdl

 bdl

**RD07 RD07A**

 **RD08N**

 **RD08NA**

 **RD08kr**

 **RD08krA**

 **RD08o**

 **RD11L RD11U**

 **RD11o BTM1 BTM1A**

 **BTM1o**

 **BTM1o2**

 **BTM1o3**

 **BTM1o4**

 **BTM2**


  *samples from depth of (below ground level), nearby vents; repeated measurement; pyrometamorphic"S" – sulfur-mineralized vent.*

*2Abbreviations explained under Table 1; ViCl – vinyl chloride; furan, pyridine and DMDS were analyzed but were below their detection limits. 3Notable(>100ppm)enrichmentgiveninbold.*

#### **Table 2.**

**vent 1**

**243**

T [oC]

H O2 2

CO2

CO N O

2

NO NO2 NH3

SO2 HCl

CCl4

HF

SiF4 AsH3 methane

propane

hexane

ethene

DCM

1,1-DCE

 12

 bdl

 bdl

 bdl

 bdl

**103**

 **102**

 **102**

 **104**

bdl

 bdl

 11

 2.4

 bdl

 bdl

 bdl

 bdl

 bdl

 30

 19

 11

 28

 20

**181**

 **191**

 **191**

 **189**

36

 39

**173**

 **143**

92

**142**

46

 76

 82

 bdl

 bdl

 bdl

 2.3

 bdl

 26

 26

 24

 8.5

 bdl

 bdl

 bdl

 bdl

 18

 19

 21

 23

 21

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 38

 69

 39

 40

**64**

**192**

72

 bdl

 bdl

 85

 34

 37

 37

 39

**208**

 **215**

11

 12

**233**

bdl

**257**

 **277**

bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 9.8

 12

**1110**

 **740**

 **1130**

 **1130**

 **880**

0.04

 0.09

 0.40

 bdl

 0.28

 bdl *aliphatic and aromatic hydrocarbons*

 bdl

 bdl

 bdl

 *and their derivatives*, *ppm*

 0.38

 0.37

 bdl

 bdl

 0.88

**2.9**

0.19

 bdl

**2.9**

bdl

 0.08

 2.4

 2.5

 0.18

 48

 48

 47

 47

 3.0

 3.5

 0.42

 bdl

 25

 15

 28

 26

 10

 0.19

 bdl

 bdl

 1.1

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

0.57

 0.03

 0.06

 bdl

 0.11

 bdl

 bdl

 bdl

 bdl

 0.34

 0.34

 bdl

 bdl

 6.0

 8.5

 8.5

 8.2

 4.0

 0.48

 0.73

 2.9

 2.7

 0.94

 8.4

 8.3

 8.3

 8.3

 3.7

 3.9

 0.71

 1.2

 4.3

 1.2

 5.6

 5.9

 4.9

bdl

 15

 46

 bdl

 14

 79

 59

 58

 53

 39

 47

**129**

 **172**

bdl

 bdl

 bdl

**123**

bdl

1.5

 3.1

 4.1

 3.1

 3.0

 bdl

 bdl

 bdl

 bdl

 2.0

 1.4

 12

 bdl

 8.3

 bdl

 bdl

 bdl

 8.3

bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 66

 bdl

 bdl

 31

12

 15

 bdl

 bdl

 19

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

**100**

bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 1.3

 1.3

 1.3

 1.2

 bdl

 bdl

 bdl

 2.6

 bdl

 bdl

 bdl

 bdl

 bdl

92

**143**

 **166**

 **164**

 **144**

 **1090**

 **1070**

 **1060**

 **1040**

 **172**

 **176**

21

 21

**1220 12600**

 **938**

 **952 26700**

bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl *inorganics, ppm*

 bdl

 bdl

 0.11

 0.79

 38.31

 33.95

 34.75

 25.77

 38.41

*Fossil Fuel Fires: A Forgotten Factor of Air Quality DOI: http://dx.doi.org/10.5772/intechopen.96294*

2.47

 3.91

 4.38

 4.29

 3.98

 6.42

 6.37

 6.24

 6.37

 4.43

 4.50

 7.28

 7.81

 25.63

 22.56

 25.53

 21.52

 21.13

 45

 45

 100

 100

 45

 180

 180

 65

 65 **pFTIR**

*main components,*

 *vol. %*

 43

 300

 30

 49

 150

 210

 86

 86

 100

**SWC1 SWC1r SWC1oP**

 **SWC1oSW**

 **SWC1oB**

 **SWC2 SWC2o**

 **SWC2o2**

 **SWC2o3**

 **SWC3 SWC3A**

 **RCH1 RCH1A**

 **ZBB1 ZBB1A ZBB2 ZBB2o**

 **ZBB3**

*Results of the pFTIR and GC gas analyses of the "Marcel" mine BCWH in Radlin (RD, second gas study) and a heap in Bytom (BTM).*

## *Fossil Fuel Fires: A Forgotten Factor of Air Quality DOI: http://dx.doi.org/10.5772/intechopen.96294*


**vent**

**242**

benzene

toluene

EtB

*m/p*-X

*o*-X

styrene

*i*-PrB

*n*-PrB

*m*-EtT

*p*-EtT

*o*-EtT

1,3,5-TMB

1,2,4-TMB

1,2,3-TMB

*Values in parentheses* *1the "A" add denotes samples taken from the depth of 0.8–1 m (below the ground level), while "a" and "o" denote nearby vents; "r" – repeated* 

*"S" –* *2Abbreviations*

*3Notable (>100 ppm) enrichment given in bold.*

**Table 2.** *Results of the pFTIR and GC gas analyses of the*

*"Marcel" mine BCWH in Radlin (RD, second gas study) and a heap in Bytom (BTM).*

 *explained under Table 1; ViCl – vinyl chloride; furan, pyridine and DMDS were analyzed but were below their detection limits.*

*sulfur-mineralized*

 *vent.*

 *denote overrun of the upper* 

 0.01

 0.01

 0.01

 0.004

 0.002

 0.01

 0.002

 0.001

 0.001

 0.01

 0.03

 0.01

 0.16

 5.3

 **RD07 RD07A**

 **RD08N**

3.2

0.27

0.08

0.11

0.05

0.01

0.02

0.01

0.05

0.02

0.02

0.02

0.08

0.05

 0.07

 0.0001

*measurement*

 *range.*

 0.001

 0.01

 0.14

 0.17

 0.0001

 0.003

 0.02

 0.13

 0.05

 0.0001

 0.001

 0.01

 0.11

 0.04

 0.00005

 0.001

 0.01

 0.05

 0.05

 0.00003

 0.001

 0.01

 0.06

 0.11

 0.0001

 0003

 0.01

 0.08

 0.04

 0.0001

 0.002

 0.003

 0.02

 0.01

 bdl

 0.001

 0.003

 0.02

 0.005

 0.00003

 0.001

 0.01

 0.01

 0.13

 0.0004

 0.01

 0.18

 0.15

 0.28

 0.001

 0.05

 0.34

 0.36

 0.08

 0.0003

 0.02

 0.09

 0.10

 0.66

 0.005

 0.13

 1.6

 0.53

 4.3

 0.13

 0.46

 5.5

 33

21 7.6 3.6 3.0 1.1 0.14 0.71 0.27 0.54 0.38 0.25 0.38

1.0 0.55

*measurement; "P" –*

*pyrometamorphic*

 *zone,*

 **RD08NA**

 **RD08kr**

 **RD08krA**

 **RD08o**

 **RD11L RD11U RD11o BTM1 BTM1A**

 **BTM1o**

 **BTM1o2**

 **BTM1o3**

 **BTM1o4**

 **BTM2**

1.3

0.27

0.06

0.17

0.07

0.003

*Environmental Sustainability - Preparing for Tomorrow*

0.01

0.01

0.05

0.02

0.02

0.02

0.05

0.04


**vent**

**245**

propene

*i*-butane

*n*-butane

1-butene

*i*-butene

*t*-2-bu

*c-*2-bu

*i*-pentane

**vent**

*i*-pentane

*n*-pentane

isoprene

1,3-budi

*t*-2-pte

*c*-2-pte

*n*-heptane

*n*-octane

*n*-nonane

*n*-decane

2,3-DMBu

2-MPT

3-MPT

cpt

 0.0005

 9.9

 0.26

 0.02

 0.0003

 0.0003

 0.0002

 0.001

 0.0001

 0.0002

 bdl

 bdl

 0.002

 0.003

 **SWC1 SWC1r SWC1oP**

 **SWC1oSW**

 **SWC1oB**

 **SWC2 SWC2o**

 **SWC2o2**

> 0.001

0.001

bdl 0.0001 0.0004 0.0003

0.001 0.001 0.0003 0.0003

bdl 0.001 0.0002 0.0002

 **SWC2o3**

 **SWC3 SWC3A**

0.10

0.29

0.003

0.01

0.04

0.02

0.12

0.10

0.08

0.06

0.01

0.05

0.02

0.04

 0.01

 0.0005

 0.003

 0.10 0.002

 0.01

 0.0003

 0.001

 0.07 0.001

 0.03

 0.001

 0.004

 0.15 0.003

 bdl

 0.0001

 0.001

 0.02 0.001

 0.02

 0.00004

 0.001

 0.04 0.0002

 0.03

 0.00004

 0.001

 0.07 0.003

 0.05

 0.0001

 0.001

 0.18 0.004

 0.07

 0.001

 0.01

 0.33

 0.01

 0.02

 0.0001

 0.0002

 0.04 0.002

 0.04

 0.0002

 0.001

 0.09

 0.01

 0.04

 bdl

 bdl

 bdl

 0.01

 bdl

 0.001

 0.00005

 0.01 0.001

 0.14

 0.005

 0.03

 0.96

 0.03

 0.04

 0.002

 0.01

 0.34

 0.01

 **RCH1**

 **RCH1A**

 **ZBB1 ZBB1A ZBB2 ZBB2o ZBB3**

 0.003

 0.001

 0.001

 bdl

 bdl

 0.004

 0.002

 bdl

 **SWC1 SWC1r SWC1oP**

 **SWC1oSW**

 **SWC1oB**

 **SWC2 SWC2o**

 **SWC2o2**

> 0.01

0.001 0.002 0.001 0.002 0.001 0.001 0.001

 **SWC2o3**

 **SWC3 SWC3A**

0.65

0.15

0.55

0.05

0.09

0.09

0.06

0.10

 0.04

 0.14

 0.0001

 0.0001

 0.16

 0.01

 0.20

 0.0001

 0.0003

 0.28

 0.02

*Fossil Fuel Fires: A Forgotten Factor of Air Quality DOI: http://dx.doi.org/10.5772/intechopen.96294*

> 0.37

> 0.0003

> 0.0005

> 0.24

> 0.01

 0.18

 0.0002

 0.0002

 0.17

 0.02

 0.27

 0.01

 0.13

 2.0

 0.07

 0.06

 0.01

 0.03

 0.53

 0.03

 1.6

 0.001

 0.001

 1.6

 0.03

 **RCH1 RCH1A**

 **ZBB1 ZBB1A ZBB2 ZBB2o ZBB3**


## *Fossil Fuel Fires: A Forgotten Factor of Air Quality DOI: http://dx.doi.org/10.5772/intechopen.96294*

**vent 1**

**244**

1,2-DCE

1,1,1-TCE

**vent**

1,2-DCP

1,1-DCEe

VC ClB

cumene

phenol

*o*-cresole

THF

py tph

fm DMS

DMDS

**vent**

CH3Cl

COS ethyne

 0.001

 0.001

 **SWC1 SWC1r SWC1oP**

 **SWC1oSW**

 **SWC1oB**

 **SWC2 SWC2o**

 **SWC2o2**

> 0.06

0.0004

0.02

 0.24

 0.0001

 0.004

 0.02

 0.02

 **SWC2o3**

 **SWC3 SWC3A**

0.01

 0.04

 0.001 0.003

 0.01

 2.1

 0.45

 0.001

 2.0

 0.21

 **RCH1 RCH1A**

 **ZBB1 ZBB1A ZBB2 ZBB2o ZBB3**

**380**

 **289**

bdl

 16

**293**

bdl

 bdl

 bdl

**GC –**

**additional compounds**

 bdl

**322**

 **321**

7.1

 12

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 23

 17

 65

**153**

60

**148**

 **120**

1.8

 0.21

 7.1

 5.7

 0.31

 7.4

 7.5

 7.5

 9.4

 2.8

 3.1

 1.6

 1.9

 bdl

 1.2

 2.8

 bdl

 2.2

 bdl

**146**

26

 bdl

**149**

 **260**

 **204**

 **200** *other organic compounds*, *ppm*

 **194**

 **151**

 **141**

bdl

 bdl

**496**

bdl

**448**

 **282**

bdl

**178**

 **202**

19

**168**

 **206**

bdl

 bdl

 bdl

 bdl

**231**

 **232**

bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 36

 bdl

 32

 21

 bdl

 2.4

 1.6

 5.6

 2.5

 1.4

 13

 13

 12 *heterocyclic organic compounds*, *ppm*

 13

 6.2

 7.1

 56

 52

 30

 22

 39

 63

 16

 4.9

 bdl

 0.45

 9.7

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 20

 11

 34

 bdl

 36

 bdl

 bdl

 bdl

 bdl

 bdl

 66

 64

 62

 50

 bdl

 bdl

 42

 39

 90

 16

**128**

92

**153**

 9.5

 bdl

 bdl

 51

 bdl

 19

 22

 39

 24

 8.3

 7.7

 bdl

 24

 bdl

 73

 bdl

 bdl

 67

bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

**323**

 **145**

 **365**

 **299**

 **97**

*Environmental Sustainability - Preparing for Tomorrow*

 7.2

 bdl

 27

 21

 bdl

**287**

 **274**

 **272**

 **272**

30

 33

**206**

 **221**

 **166**

 **130**

 **191**

 **176**

56

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 54

 67

 61

 bdl

**214**

 **114**

bdl

 **SWC1 SWC1r**

 **SWC1oP**

 **SWC1oSW**

 **SWC1oB**

 **SWC2 SWC2o**

 **SWC2o2**

 **SWC2o3**

 **SWC3 SWC3A**

 **RCH1 RCH1A**

 **ZBB1 ZBB1A ZBB2 ZBB2o ZBB3**

 bdl

 bdl

 1.8

 bdl

 bdl

**492**

 **447**

 **444**

 **436**

bdl

 bdl

 63

 bdl

 23

 bdl

 26

 65

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 bdl

 59

 bdl

 bdl

 60

**SWC1 SWC1r SWC1oP**

 **SWC1oSW**

 **SWC1oB**

 **SWC2 SWC2o**

 **SWC2o2**

 **SWC2o3**

 **SWC3 SWC3A**

 **RCH1 RCH1A**

 **ZBB1 ZBB1A ZBB2 ZBB2o**

 **ZBB3**


*2Abbreviations explained under Table 1; ethane, furan and acetic acid were analyzed but were below their detection limits.*

8.3; SO2, 120, 31; 671, 25; 388, 160; 532, 202; 79, 40; 123, 123; HCl, 11, 2.4; 6.5, 0.58; 6.2, 3.6; 19, 6.1; 8.4, 3.0; 5.9, 3.8; CCl4, , ; 6.6, 6.6; 11, 6.5, 1.1, 1.1; 0.57, 0.15; 8.5, 6.8; HF, 0.62, 0.62; 0.03, 0.03; 0.12, 0.12; 1.1, 0.36; 1.1, 0.46; , ; SiF4, 6.3, 1.3; 31, 3.5; 21, 16; 3.2, 1.7; 48, 4.6; 28, 19; AsH3, 0.17, 0.09; 1.7, 0.38; 1.7, 0.75; 3.4, 1.7; 0.40, 0.20; 2.9, 1.1; CH4, 262, 107; 2950, 16; 3470, 1238; 819, 491; , ; 1130, 984; ethane, , ; 30, 30; 142, 142; 281, 281; , ; , ; propane, 42, 15; 729, 15; 601, 275; 694, 410; 215, 77; 277, 255; hexane, 11, 1.8; 152, 51; 139, 73; 608, 225; , ; 69, 48; ethene, 6.6, 3.2; 79, 6.9; 12, 6.0; 84, 27; 26, 13; 23, 20; DCM, 141, 36; 368, 69; 126, 47; 84, 46; 191, 51; 142, 82; 1,1-DCE, 7.2, 7.2; 17, 8.9; , ; 16, 16; 104, 67; , ; 1,2-DCE, , ; 77, 77; 39, 39; 38, 38; , ; 60, 59; 1,1,1-TCE, 99, 46; 417, 26; 36, 25; 59, 11; 492, 150; 65, 34; 1,2-DCP, 31, 31; 56, 56; 384, 159; 568, 226; , ; 214, 114; 1,1-DCEe, 77, 21; 347, 67; 195, 123; 28, 17; 287, 66; 191, 132; vinyl chloride, , ; , ; 416, 235; chlorobenzene, 39, 24; 186, 15; 77, 44; 206, 81; 51, 18; 73, 70; cumene, 34, 16; 399, 5.7; 126, 97; 264, 81; 66, 81; 153, 60; 153, 76; phenol, 29, 10; 7, 4.2; 51, 16; 67, 41; 9.7, 2.8; 36, 23; *o*-cresol, 46, 5.8; 66, 3.6; 65, 36; 81, 54; 13, 5.3; 63, 30; furan, 0.14, 0.14 (no records for other sites); THF, 1.3, 0.41; 177, 177; 96, 12; 293, 261; , ; 36, 29; thiophene, 192, 146; 173, 38; 556, 332; 689, 241; 260, 143; 496, 397; formaldehyde, 12, 3.7; 13, 1.2; 5.5, 2.0; 17, 2.3; 9.4, 3.0; 2.8, 1.9; acetic acid, , ; , ; 9.1, 9.1; 50, 14; , ; , ; DMS, 62, 21; 893, 28; 401, 69; 1540, 534; , ; 153, 101; DMDS, 104, 28; 37, 21; , ; , ; 380, 194; , ; ad pyridine, 7.1, 7.1; 86, 7.3; , ; , ; 232, 144; , [ppm]. As compared to these vents, the one at the RCH site. The geometric mean concentrations for the whole range are: H2O 9.5, CO2 3.83 [vol.%], CO 350, NO 20, NO2 54, N2O 0.51, NH3 7.5, SO2 72, HCl 2.5, CCl4 2.3, HF 0.26, SiF4 4.5, AsH3 0.53, methane 201, ethane 106, propane 58, hexane 29, ethene 11, DCM 54, 1,1-DCE 17, 1,2-DCE 53, 1,1,1-TCE 37, 1,2-DCP 127, 1,1-DCEe 60, vinyl chloride 165, chlorobenzene 30, cumene 36, phenol and *o*-cresol and THF 13, furan 0.14, thiophene 200,

*Fossil Fuel Fires: A Forgotten Factor of Air Quality DOI: http://dx.doi.org/10.5772/intechopen.96294*

formaldehyde 2.2, acetic acid 13, DMS 65, DMDS 39, and pyridine 29.

In general, the data provided for additional vents from additional BCWH probed

allows to enlarge the span of the maximum observed values of only some compounds. They include (with excess in parentheses) CO (10x), SO2, 1,1,1-TCE (12x), 1,1-DCEe (2.5x), cumene (2x), formaldehyde (3x), and pyridine (21x). Higher than previously observed geometric mean values are also observed for NO2, CCl4, ethane (2x), propane, ethene, and thiophene. This is clearly seen in the case of the latter two compounds, with more frequent positive determinations than within the previous studies. Similar levels of geometric means are found for HCl, AsH3, chlorobenzene, phenol, and DMDS. As formerly observed, concentration ranges are usually extremely variable. Cumene is a good example of a compound with very high maximum but very low geometric mean. So is true, though less clearly, for, e.g., *o*-cresol. Some compounds often show large contents but single records. For many BCWHs there are large discrepancies between the geometric mean values and maximums, while for less number of the objects studied the amounts emitted are at very steady level. Some constituents, like vinyl chloride and even methane, may show very high concentrations (>100 ppm) but may be "absent" (below detection limits) at other BCWHs or vents. As explained in the former papers, this results from very high dynamics of the local combustion processes. The *ex situ* GC values obtained are, again, usually much lower than those observed by *in situ* FTIR, thus confirming their uncertain and, possibly, semi-quantitative value. On the other hand, two compounds not observed within the previous GC data are now determined: CH3Cl (chloromethane or methyl chloride) and cyclopentane.

**5. Discussion**

**247**

*3Notable (>100 ppm) enrichment given in bold.*

#### **Table 3.**

*Results of the pFTIR and GC gas analyses of a BCWH in Świętochłowice (SWC), "Starzykowiec" heap of the "Chwałowice" mine in Rybnik (RCH), and "Ruda" heap in Zabrze-Biskupice (ZBB).* 8.3; SO2, 120, 31; 671, 25; 388, 160; 532, 202; 79, 40; 123, 123; HCl, 11, 2.4; 6.5, 0.58; 6.2, 3.6; 19, 6.1; 8.4, 3.0; 5.9, 3.8; CCl4, , ; 6.6, 6.6; 11, 6.5, 1.1, 1.1; 0.57, 0.15; 8.5, 6.8; HF, 0.62, 0.62; 0.03, 0.03; 0.12, 0.12; 1.1, 0.36; 1.1, 0.46; , ; SiF4, 6.3, 1.3; 31, 3.5; 21, 16; 3.2, 1.7; 48, 4.6; 28, 19; AsH3, 0.17, 0.09; 1.7, 0.38; 1.7, 0.75; 3.4, 1.7; 0.40, 0.20; 2.9, 1.1; CH4, 262, 107; 2950, 16; 3470, 1238; 819, 491; , ; 1130, 984; ethane, , ; 30, 30; 142, 142; 281, 281; , ; , ; propane, 42, 15; 729, 15; 601, 275; 694, 410; 215, 77; 277, 255; hexane, 11, 1.8; 152, 51; 139, 73; 608, 225; , ; 69, 48; ethene, 6.6, 3.2; 79, 6.9; 12, 6.0; 84, 27; 26, 13; 23, 20; DCM, 141, 36; 368, 69; 126, 47; 84, 46; 191, 51; 142, 82; 1,1-DCE, 7.2, 7.2; 17, 8.9; , ; 16, 16; 104, 67; , ; 1,2-DCE, , ; 77, 77; 39, 39; 38, 38; , ; 60, 59; 1,1,1-TCE, 99, 46; 417, 26; 36, 25; 59, 11; 492, 150; 65, 34; 1,2-DCP, 31, 31; 56, 56; 384, 159; 568, 226; , ; 214, 114; 1,1-DCEe, 77, 21; 347, 67; 195, 123; 28, 17; 287, 66; 191, 132; vinyl chloride, , ; , ; 416, 235; chlorobenzene, 39, 24; 186, 15; 77, 44; 206, 81; 51, 18; 73, 70; cumene, 34, 16; 399, 5.7; 126, 97; 264, 81; 66, 81; 153, 60; 153, 76; phenol, 29, 10; 7, 4.2; 51, 16; 67, 41; 9.7, 2.8; 36, 23; *o*-cresol, 46, 5.8; 66, 3.6; 65, 36; 81, 54; 13, 5.3; 63, 30; furan, 0.14, 0.14 (no records for other sites); THF, 1.3, 0.41; 177, 177; 96, 12; 293, 261; , ; 36, 29; thiophene, 192, 146; 173, 38; 556, 332; 689, 241; 260, 143; 496, 397; formaldehyde, 12, 3.7; 13, 1.2; 5.5, 2.0; 17, 2.3; 9.4, 3.0; 2.8, 1.9; acetic acid, , ; , ; 9.1, 9.1; 50, 14; , ; , ; DMS, 62, 21; 893, 28; 401, 69; 1540, 534; , ; 153, 101; DMDS, 104, 28; 37, 21; , ; , ; 380, 194; , ; ad pyridine, 7.1, 7.1; 86, 7.3; , ; , ; 232, 144; , [ppm]. As compared to these vents, the one at the RCH site. The geometric mean concentrations for the whole range are: H2O 9.5, CO2 3.83 [vol.%], CO 350, NO 20, NO2 54, N2O 0.51, NH3 7.5, SO2 72, HCl 2.5, CCl4 2.3, HF 0.26, SiF4 4.5, AsH3 0.53, methane 201, ethane 106, propane 58, hexane 29, ethene 11, DCM 54, 1,1-DCE 17, 1,2-DCE 53, 1,1,1-TCE 37, 1,2-DCP 127, 1,1-DCEe 60, vinyl chloride 165, chlorobenzene 30, cumene 36, phenol and *o*-cresol and THF 13, furan 0.14, thiophene 200, formaldehyde 2.2, acetic acid 13, DMS 65, DMDS 39, and pyridine 29.

## **5. Discussion**

In general, the data provided for additional vents from additional BCWH probed allows to enlarge the span of the maximum observed values of only some compounds. They include (with excess in parentheses) CO (10x), SO2, 1,1,1-TCE (12x), 1,1-DCEe (2.5x), cumene (2x), formaldehyde (3x), and pyridine (21x). Higher than previously observed geometric mean values are also observed for NO2, CCl4, ethane (2x), propane, ethene, and thiophene. This is clearly seen in the case of the latter two compounds, with more frequent positive determinations than within the previous studies. Similar levels of geometric means are found for HCl, AsH3, chlorobenzene, phenol, and DMDS. As formerly observed, concentration ranges are usually extremely variable. Cumene is a good example of a compound with very high maximum but very low geometric mean. So is true, though less clearly, for, e.g., *o*-cresol. Some compounds often show large contents but single records. For many BCWHs there are large discrepancies between the geometric mean values and maximums, while for less number of the objects studied the amounts emitted are at very steady level. Some constituents, like vinyl chloride and even methane, may show very high concentrations (>100 ppm) but may be "absent" (below detection limits) at other BCWHs or vents. As explained in the former papers, this results from very high dynamics of the local combustion processes. The *ex situ* GC values obtained are, again, usually much lower than those observed by *in situ* FTIR, thus confirming their uncertain and, possibly, semi-quantitative value. On the other hand, two compounds not observed within the previous GC data are now determined: CH3Cl (chloromethane or methyl chloride) and cyclopentane.

**vent**

**246**

benzene

toluene

EtB

*m/p*-X

*o*-X

styrene

*i*-PrB

*n*-PrB

*m*-EtT

*p*-EtT

*o*-EtT

1,3,5-

0.001

TMB

1,2,4-

0.001

TMB

1,2,3-

0.0004

TMB

*Values in parentheses denote overrun of the upper measurement*

*1The "A" add denotes samples taken from the depth of 0.8–1 m (below the ground level), while "a" and "o" denote nearby vents; "r" – repeated measurement; "P" –*

*2Abbreviations*

*3Notable (>100 ppm) enrichment given in bold.*

**Table 3.** *Results of the pFTIR and GC gas analyses of a BCWH in*

*(ZBB).*

*Świętochłowice*

 *(SWC),*

*"Starzykowiec"*

 *heap of the*

*"Chwałowice" mine in Rybnik (RCH), and*

*"Ruda" heap in* 

*Zabrze-Biskupice*

 *explained under Table 1; ethane, furan and acetic acid were analyzed but were below their detection limits.*

 *range.*

 0.0002

 0.0004

 0.001

 0.0004

 0.0002

 bdl

 0.001

 0.001

 0.0004

 0.01

 0.0001

 **SWC1 SWC1r SWC1oP**

 **SWC1oSW**

 **SWC1oB**

 **SWC2 SWC2o**

 **SWC2o2**

> 0.03

0.005 0.001 0.002 0.001

bdl bdl 0.0004 0.0002 0.0001 0.0001

bdl 0.0004 0.0002

0.01

 0.01

 0.0002

 0.001

 0.03 0.004

*pyrometamorphic*

 *zone, "S" –*

*sulfur-mineralized*

 *vent.*

0.02

 0.03

 0.0005

 0.001

 0.05

 0.01

 **SWC2o3**

 **SWC3 SWC3A**

0.50

0.22

0.03

0.07

0.03

0.003

0.002

0.01

0.01

0.004

0.01

0.01

 0.01

 0.0001

 0.0004

 0.01 0.001

 0.01

 0.0001

 0.0004

 0.02 0.001

 0.01

 0.0001

 0.001

 0.02 0.001

 0.02

 0.0003

 0.001

 0.04 0.003

 0.01

 0.0001

 0.0003

 0.02 0.001

 0.004

 0.00002

 0.0002

 0.003 0.001

 bdl

 0.00002

 0.0003

 0.02 0.0004

*Environmental Sustainability - Preparing for Tomorrow*

 0.06

 0.001

 0.001

 0.13 0.005

 0.15

 0.002

 0.002

 0.34

 0.01

 0.04

 0.001

 0.001

 0.09 0.004

 0.41

 0.002

 0.002

 2.7

 0.01

 1.7

 0.003

 0.46

 12

 33

 **RCH1**

 **RCH1A**

 **ZBB1 ZBB1A ZBB2 ZBB2o ZBB3**

At the time of the BCWH gas analyses the author could not find paper showing the usage of FTIR for environmental studies. Stockwell et al. [27] used this method to measure H2O, COx, NOx, HCl, SO2, NH3, methane, acetylene, ethene, propane, formaldehyde, formic acid, methanol, acetic acid, HCN, furan, glycolaldehyde, and HONO (the latter also initially reported in [6]) in biomass emissions, though in a Fire Lab at Missoula Experiment. A more *in situ* type of work, engaging airborne FTIR, is by Yokelson et al. [28] who measured African savanna fires, with 14 compounds analyzed.

**References**

669–705.

135–138 [in Polish].

312 pp.

91–96.

3723–3731.

**249**

[1] Nasdala, L., Pekov, I.V., 1993. Ravatite, C14H10, a new organic mineral species from Ravat, Tadzhikistan. European Journal of Mineralogy, 6,

*Fossil Fuel Fires: A Forgotten Factor of Air Quality DOI: http://dx.doi.org/10.5772/intechopen.96294*

> Silesian materials. Science of the Total Environment, 640-641, 1044–1071.

[7] Wickenheiser, B., Michalke, K., Hensel, R., Drescher, C., Hirner, A.V., Rutishauser, B., Bachofen, R., 1998. Volatile compounds in gases emitted from the wetland bogs near Lake Cadagno. In: Peduzzi, R., Bachofen, R., Tonolla, M. (Eds), Lake Cadagno: a meromictic Alpine lake. Documenta dell'Istituto italiano di idrobiologia, 63,

137–140.

415 pp.

[8] Craig, P.J. (ed), 2003.

Organometallic Compounds in the Environment, 2nd ed. John Wiley & Sons Ltd., Chichester, West Sussex, UK,

[9] Khoury, J., Lewis, R., Sattler, A., Linsley, B., Magers, K., Lee, J., 2008. Analysis of volatile arsenic compounds in landfill gas. WEF/A&WMA Odors and Air Emissions 2008, Water Environment Federation, 630–641.

[10] Kruszewski, Ł., 2013a. Komora termiczna jako narzędzie do

zrozumienia procesów przeobrażenia materiałów odpadowych [Thermal chamber as a tool for understanding the processes of trasformation of waste materials; presented on: 4th Meeting of the Users of the Bruker Systems]. IV Spotkanie Użytkowników Systemów Firmy Bruker, Poznań 03–04.10.2013,

59–60 [poster #6; in Polish].

[11] Kruszewski Ł., 2013b: Supergene sulphate minerals from the burning coal mining dumps in the Upper Silesian Coal Basin, South Poland. International Journal of Coal Geology, 105, 91–109.

[12] Kruszewski, Ł., Fabiańska, M.J., Segit, T., Kusy, D., Motyliński, R., Ciesielczuk, J., Deput, E., 2020. Carbon-

nitrogen compounds, alcohols, mercaptans, monoterpenes, acetates, aldehydes, ketones, SF6, PH3, and other

[2] Cebulak, S., Smieja-Król, B., Tabor, A., Misz, M., Jelonek, I., Jelonek, Z., 2005. Oxyreactive Thermal Analysis (OTA) – A Good and Cheap Method of the Estimation of Coal Self-Ignition in Bingsteads – Preliminary Research Results. Geological Publishing Houses (Geological Institute, Warsaw, Poland),

[3] Sokol, E.V., Maksimova, N.V., Nigmatulina, E.N., Sharygin, V.V., Kalugin, V.M., 2005. Combustion Metamorphism. Publishing House of the

SB RAS, Novosibirsk, Russia [in Russian, with fragments in English],

[5] Colman, J.J., Swanson, A.L., Meinardi, S., Sive, B.C., Blake, D.R., Rowland, F.S., 2001. Description of the Analysis of a Wide Range of Volatile Organic Compounds in Whole Air Samples Collected During PEM-Tropics A and B. Analytical Chemistry, A-I. American Chemical Society, 73(15),

[6] Kruszewski, Ł., Fabiańska, M.J., Ciesielczuk, J., Segit, T., Orłowski, R., Motyliński, R., Moszumańska, I., Kusy, D. 2018. 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

[4] Stracher, G.B., 2007. The origin of gas-vent minerals: isochemical and mass-transfer processes. In: Stracher, G. B. (ed.), Geology of Coal Fires: Case Studies from Around the World, v. 18. The Geological Society of America, Reviews in Engineering Geology, USA,

It is noteworthy that numerous organic and organo(semi)metallic compounds (or similar ones) detected in the BCWHs exhausts are also detected in volcanic fumaroles (mainly via GC, or modeled, as summarized by Wahrenberger [29]) or algal emissions (by GC–MS; [30]). Examples of interesting species include CO2, COS, CS2, S2, S8, SO2, AsH3, HCl, HF, HBr, CHCl3, NO2, propanal, methanol, acetaldehyde, 1,1,2-trichlorotrifluoroethane, hexafluoropropene, tetrachloroethene, vinyl chloride, *i*-butene, hexane, octane, octane, butadiene, benzene, toluene, α-pinene, *i*- and *n*-propanol, methylacrolein, MEK, acetone, 1,4-dioxane, dimethyldifluorosilane, thioformaldehyde, ethylthiophene, trimethylborane, methylphosphine, and uncertain [*N*-(phenyl-2-pyridinylmethylene)benzeneamine-*N*,*N*<sup>0</sup> ]-irontricarbonyl and silver benzoate; geosmin, cyclopentane, cyclohexane, acetic acid, acetamide, glucopyranose, dibutyl phthalate, cholest-5-en-22-one, benzaldehyde, hydrazine, 8-amino-2-naphthalenol, ethanethioimide, thiourea, 1,3-oxathian-2-one, tetrahydro-2,5-dimethylthiophene, 6-methylbenzo[*b*]thiophene, 3,3,5,5,-tetramethyl-1,2,4-trithiolane, thiirane, C2H7O2B borane, trimethylsilane, butytrimethylsilane, or undecanoic acid 11-chloro- and 11-fluorotrimethylsilyl esters.

## **Acknowledgements**

This work was financed by the NCN (Narodowe Centrum Nauki, or National Science Centre) grant no. 2013/11/B/ST10/04960.

### **Author details**

Łukasz Kruszewski Institute of Geological Sciences, Polish Academy of Sciences, Warszawa, Poland

\*Address all correspondence to: lkruszewski@twarda.pan.pl

© 2021 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/ by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

*Fossil Fuel Fires: A Forgotten Factor of Air Quality DOI: http://dx.doi.org/10.5772/intechopen.96294*

## **References**

At the time of the BCWH gas analyses the author could not find paper showing the usage of FTIR for environmental studies. Stockwell et al. [27] used this method to measure H2O, COx, NOx, HCl, SO2, NH3, methane, acetylene, ethene, propane, formaldehyde, formic acid, methanol, acetic acid, HCN, furan, glycolaldehyde, and HONO (the latter also initially reported in [6]) in biomass emissions, though in a Fire Lab at Missoula Experiment. A more *in situ* type of work, engaging airborne FTIR, is by Yokelson et al. [28] who measured African savanna fires, with 14

It is noteworthy that numerous organic and organo(semi)metallic compounds (or similar ones) detected in the BCWHs exhausts are also detected in volcanic fumaroles (mainly via GC, or modeled, as summarized by Wahrenberger [29]) or algal emissions (by GC–MS; [30]). Examples of interesting species include CO2, COS, CS2, S2, S8, SO2, AsH3, HCl, HF, HBr, CHCl3, NO2, propanal, methanol, acetaldehyde, 1,1,2-trichlorotrifluoroethane, hexafluoropropene, tetrachloroethene, vinyl chloride, *i*-butene, hexane, octane, octane, butadiene, benzene, toluene, α-pinene, *i*- and *n*-propanol, methylacrolein, MEK, acetone, 1,4-dioxane, dimethyldifluorosilane, thioformaldehyde, ethylthiophene, trimethylborane, methylphosphine, and uncertain [*N*-(phenyl-2-pyridinylmethylene)benzeneamine-

]-irontricarbonyl and silver benzoate; geosmin, cyclopentane, cyclohexane, acetic acid, acetamide, glucopyranose, dibutyl phthalate, cholest-5-en-22-one, benzaldehyde, hydrazine, 8-amino-2-naphthalenol, ethanethioimide, thiourea, 1,3-oxathian-2-one, tetrahydro-2,5-dimethylthiophene, 6-methylbenzo[*b*]thiophene, 3,3,5,5,-tetramethyl-1,2,4-trithiolane, thiirane, C2H7O2B borane, trimethylsilane, butytrimethylsilane, or undecanoic acid 11-chloro- and

This work was financed by the NCN (Narodowe Centrum Nauki, or National

Institute of Geological Sciences, Polish Academy of Sciences, Warszawa, Poland

© 2021 The Author(s). Licensee IntechOpen. This chapter is distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/ by/3.0), which permits unrestricted use, distribution, and reproduction in any medium,

\*Address all correspondence to: lkruszewski@twarda.pan.pl

provided the original work is properly cited.

compounds analyzed.

*Environmental Sustainability - Preparing for Tomorrow*

11-fluorotrimethylsilyl esters.

Science Centre) grant no. 2013/11/B/ST10/04960.

**Acknowledgements**

**Author details**

**248**

Łukasz Kruszewski

*N*,*N*<sup>0</sup>

[1] Nasdala, L., Pekov, I.V., 1993. Ravatite, C14H10, a new organic mineral species from Ravat, Tadzhikistan. European Journal of Mineralogy, 6, 669–705.

[2] Cebulak, S., Smieja-Król, B., Tabor, A., Misz, M., Jelonek, I., Jelonek, Z., 2005. Oxyreactive Thermal Analysis (OTA) – A Good and Cheap Method of the Estimation of Coal Self-Ignition in Bingsteads – Preliminary Research Results. Geological Publishing Houses (Geological Institute, Warsaw, Poland), 135–138 [in Polish].

[3] Sokol, E.V., Maksimova, N.V., Nigmatulina, E.N., Sharygin, V.V., Kalugin, V.M., 2005. Combustion Metamorphism. Publishing House of the SB RAS, Novosibirsk, Russia [in Russian, with fragments in English], 312 pp.

[4] Stracher, G.B., 2007. The origin of gas-vent minerals: isochemical and mass-transfer processes. In: Stracher, G. B. (ed.), Geology of Coal Fires: Case Studies from Around the World, v. 18. The Geological Society of America, Reviews in Engineering Geology, USA, 91–96.

[5] Colman, J.J., Swanson, A.L., Meinardi, S., Sive, B.C., Blake, D.R., Rowland, F.S., 2001. Description of the Analysis of a Wide Range of Volatile Organic Compounds in Whole Air Samples Collected During PEM-Tropics A and B. Analytical Chemistry, A-I. American Chemical Society, 73(15), 3723–3731.

[6] Kruszewski, Ł., Fabiańska, M.J., Ciesielczuk, J., Segit, T., Orłowski, R., Motyliński, R., Moszumańska, I., Kusy, D. 2018. 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. Science of the Total Environment, 640-641, 1044–1071.

[7] Wickenheiser, B., Michalke, K., Hensel, R., Drescher, C., Hirner, A.V., Rutishauser, B., Bachofen, R., 1998. Volatile compounds in gases emitted from the wetland bogs near Lake Cadagno. In: Peduzzi, R., Bachofen, R., Tonolla, M. (Eds), Lake Cadagno: a meromictic Alpine lake. Documenta dell'Istituto italiano di idrobiologia, 63, 137–140.

[8] Craig, P.J. (ed), 2003. Organometallic Compounds in the Environment, 2nd ed. John Wiley & Sons Ltd., Chichester, West Sussex, UK, 415 pp.

[9] Khoury, J., Lewis, R., Sattler, A., Linsley, B., Magers, K., Lee, J., 2008. Analysis of volatile arsenic compounds in landfill gas. WEF/A&WMA Odors and Air Emissions 2008, Water Environment Federation, 630–641.

[10] Kruszewski, Ł., 2013a. Komora termiczna jako narzędzie do zrozumienia procesów przeobrażenia materiałów odpadowych [Thermal chamber as a tool for understanding the processes of trasformation of waste materials; presented on: 4th Meeting of the Users of the Bruker Systems]. IV Spotkanie Użytkowników Systemów Firmy Bruker, Poznań 03–04.10.2013, 59–60 [poster #6; in Polish].

[11] Kruszewski Ł., 2013b: Supergene sulphate minerals from the burning coal mining dumps in the Upper Silesian Coal Basin, South Poland. International Journal of Coal Geology, 105, 91–109.

[12] Kruszewski, Ł., Fabiańska, M.J., Segit, T., Kusy, D., Motyliński, R., Ciesielczuk, J., Deput, E., 2020. 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 extrernal database approach. Science of the Total Environment, 698, 134274.

[13] Kruszewski Ł. 2006. Oldhamitepericlase-portlandite-fluorite assemblage and coexisting minerals of burnt dump in Siemianowice Śląskie – Dąbrówka Wielka area (Upper Silesia, Poland) – preliminary report. Mineralogia Polonica, 28, 118–120.

[14] Kruszewski Ł. 2008: Apatiteellestadite solid solution and associated minerals of metacarbonate slags from burning coal dump in Rydułtowy (Upper Silesia). Mineralogia Special Papers, 32, 100.

[15] Kruszewski, Ł., Ciesielczuk, J., Misz-Kennan, M., 2014a. Mineralogy of some metacarbonate rocks from burned coal-mining dump in Przygórze (Lower Silesian Coal Basin) and its analogy to "olive" rocks from the Hatrurim Formation. 4th Central-European Mineralogical Conference - CEMC 2014 (Proceedings of the international symposium CEMC 2014; ISBN 978–80– 210-6832-2), p. 77.

[16] Kruszewski, Ł., Ciesielczuk, J., Misz-Kennan, M., Fabiańska, M., 2014b. Chemical composition of glasses and associating mineral species in various pyrometamorphic rocks from coalmining dumps of the Lower Silesia. Mineralogia – Special Papers, 42, 70–71.

[17] Kruszewski, Ł., 2012. Unique chloride assemblage of exhalative origin from burning coal mining dump in Radlin (Rybnik Coal Area, S Poland). Mineralogia – Special Papers 40, 90–92.

[18] Fabiańska M., Ciesielczuk J., Kruszewski Ł., Misz-Kennan M., Blake D.R., Stracher G., Moszumańska I. 2013: Gaseous compounds and efflorescences generated in self-heating coal-waste

dumps – A case study from the Upperand Lower Silesian Coal Basins (Poland). International Journal of Coal Geology, 116-117, 247–261.

versus biological activity – a potential model for survivability in a harsh environment?; Life Origins, COST Workshop 2018, Bertinoro, Italy, March

*Fossil Fuel Fires: A Forgotten Factor of Air Quality DOI: http://dx.doi.org/10.5772/intechopen.96294*

> [29] Wahrenberger, C.M., 1997. Some aspects of the chemistry of volcanic gases. Ph.D. thesis, Swiss Federal Institute of Technology, Zurich,

[30] Ali, G., 2004. Identification of volatile organic compounds produced by algae. Egyptian Journal of Phycology,

Switzerland, 233 pp.

5, 71–81.

[25] Myhre, G., Shindell, D., Breón, F.- M., Collins, W., Fuglestvedt, J., Huang, J., Koch, D., Lamarque, J.-F., Lee, D., Mendoza, B., Nakajima, T., Robock, A., Stephens, G., Takemura, T., Zhang, H. 2013. Antrhropogenic and natural radiative forcing. Chpt. 8, in: Stocker, T. F., Qin, D., Plattner, G.-K., Tignor, M., Allen, S.K., Boschung, J., Nauels, A., Xia, Y., Bex, V., Midgley, P.M. (eds), Climate Change 2013: The Physical Science Basis. Contribution of the Working Group I to the Fifth Assessment Report of the

Intergovernmental Panel on Climate Changes, Cambridge University Press, Cambride, UK, and New York, NY, USA, www.ghghprotocol.org, 640–659.

[26] ESRL, 2019. Earth System Research Laboratory GMD (Global Monitoring Division), www.esrl.noaa.gov/mgd/dv/

iadv (accessed on 08.03.2019).

[27] Stockwell, C.E., Yokelson, R.J., Kreidenweis, S.M., Robinson, A.L., DeMott, P.J., Sullivan, R.C., Reardon, J., Ryan, K.C., Griffith, D.W.T., Stevens, L., 2014. Trace gas emissions from combustion of peat, crop residue, domestic biofuels, grasses, and other fuels: configuration and Fourier transform infrared (FTIR)

component of the fourth Fire Lab at Missoula Experiment (FLAME-4). Atmospheric Chemistry and Physics, 14,

[28] Yokelson, R.J., Bertschi, I.T.,

Hao, W.M., 2003. Trace gas

Christian, T.J., Hobbs, P.V., Ward, D.E.,

measurements in nascent, aged, and cloud-processed smoke from African savanna fires by airborne Fourier transform infrared spectroscopy (AFTIR). Journal of Geophysical Researchm 108(D13), 8478.

9727–9754.

**251**

19–23 (poster, unpublished).

[19] Kruszewski, Ł., Sierny, W., 2019. Radlin coal fire heap: thiosulfate- and dithionate-bearing alkaline mineralization; Cu, Fe, As, and P mineralization; and second worldwide occurrence of tsaregorodtsevite. Mineralogia – Special Papers, 49, 54.

[20] Fabiańska, M., Ciesielczuk, J., Nádudvári, Á., Misz-Kennan, M., Kowalski, A., Kruszewski, Ł., 2019. Environmental influence of gaseous emissions from self-heating coal waste dumps in Silesia, Poland. Environmental Geochemistry and Health, 41(2), 575–601.

[21] Lewińska-Preis, L., Szram, E., Fabiańska, M., Nádudvari, Á., Misz-Kennan, M., Abramowicz, A., Kruszewski, Ł., Kita, A., 2020. Selected ions and major- and trace elements as contaminants in coal-waste dump water from the Lower- and Upper Silesian Coal Basins (Poland). International Journal of Coal Science and Technology, DOI: 10.21203/rs.3.rs-35061/v1 (preprint).

[22] Kruszewski, Ł., Ciesielczuk, J., and Misz-Kennan, M., 2012. What have meteorites to do with coal fires? A case of Upper and Lower Silesian Coal Basins. Mineralogia – Special Papers 40, 28–29.

[23] Kruszewski Ł., Fabiańska, M., Ciesielczuk, J., Segit, T., 2017. Coal fires – Titan – interstellar medium – life: what do they have in common? Potential gaseous bio-precursors in burning mining heaps. Life Origins 2017 conference (Early Earth and ExoEarths: origin and evolution of life), Book of Abstracts, 51–52.

[24] Kruszewski, Ł., Matlakowska, R., 2018. Burning coal-mining waste heaps *Fossil Fuel Fires: A Forgotten Factor of Air Quality DOI: http://dx.doi.org/10.5772/intechopen.96294*

versus biological activity – a potential model for survivability in a harsh environment?; Life Origins, COST Workshop 2018, Bertinoro, Italy, March 19–23 (poster, unpublished).

fire gases in coal-mining waste heaps of Upper Silesian Coal Basin (Poland) – a re-investigation by means of in-situ FTIR extrernal database approach. Science of the Total Environment, 698,

*Environmental Sustainability - Preparing for Tomorrow*

dumps – A case study from the Upper-

(Poland). International Journal of Coal

[19] Kruszewski, Ł., Sierny, W., 2019. Radlin coal fire heap: thiosulfate- and

[20] Fabiańska, M., Ciesielczuk, J., Nádudvári, Á., Misz-Kennan, M., Kowalski, A., Kruszewski, Ł., 2019. Environmental influence of gaseous emissions from self-heating coal waste dumps in Silesia, Poland. Environmental Geochemistry and Health, 41(2),

[21] Lewińska-Preis, L., Szram, E., Fabiańska, M., Nádudvari, Á., Misz-Kennan, M., Abramowicz, A.,

DOI: 10.21203/rs.3.rs-35061/v1

Kruszewski, Ł., Kita, A., 2020. Selected ions and major- and trace elements as contaminants in coal-waste dump water from the Lower- and Upper Silesian Coal Basins (Poland). International Journal of Coal Science and Technology,

[22] Kruszewski, Ł., Ciesielczuk, J., and Misz-Kennan, M., 2012. What have meteorites to do with coal fires? A case of Upper and Lower Silesian Coal Basins. Mineralogia – Special Papers 40,

[23] Kruszewski Ł., Fabiańska, M., Ciesielczuk, J., Segit, T., 2017. Coal fires – Titan – interstellar medium – life: what do they have in common? Potential gaseous bio-precursors in burning mining heaps. Life Origins 2017

conference (Early Earth and ExoEarths: origin and evolution of life), Book of

[24] Kruszewski, Ł., Matlakowska, R., 2018. Burning coal-mining waste heaps

and Lower Silesian Coal Basins

Geology, 116-117, 247–261.

dithionate-bearing alkaline mineralization; Cu, Fe, As, and P mineralization; and second worldwide occurrence of tsaregorodtsevite. Mineralogia – Special Papers, 49, 54.

575–601.

(preprint).

28–29.

Abstracts, 51–52.

[13] Kruszewski Ł. 2006. Oldhamite-

assemblage and coexisting minerals of burnt dump in Siemianowice Śląskie – Dąbrówka Wielka area (Upper Silesia,

periclase-portlandite-fluorite

Poland) – preliminary report. Mineralogia Polonica, 28, 118–120.

Papers, 32, 100.

210-6832-2), p. 77.

[14] Kruszewski Ł. 2008: Apatiteellestadite solid solution and associated minerals of metacarbonate slags from burning coal dump in Rydułtowy (Upper Silesia). Mineralogia Special

[15] Kruszewski, Ł., Ciesielczuk, J., Misz-Kennan, M., 2014a. Mineralogy of some metacarbonate rocks from burned coal-mining dump in Przygórze (Lower Silesian Coal Basin) and its analogy to "olive" rocks from the Hatrurim Formation. 4th Central-European Mineralogical Conference - CEMC 2014 (Proceedings of the international symposium CEMC 2014; ISBN 978–80–

[16] Kruszewski, Ł., Ciesielczuk, J., Misz-Kennan, M., Fabiańska, M., 2014b. Chemical composition of glasses and associating mineral species in various pyrometamorphic rocks from coalmining dumps of the Lower Silesia. Mineralogia – Special Papers, 42, 70–71.

[17] Kruszewski, Ł., 2012. Unique chloride assemblage of exhalative origin from burning coal mining dump in Radlin (Rybnik Coal Area, S Poland). Mineralogia – Special Papers 40, 90–92.

[18] Fabiańska M., Ciesielczuk J., Kruszewski Ł., Misz-Kennan M., Blake D.R., Stracher G., Moszumańska I. 2013: Gaseous compounds and efflorescences generated in self-heating coal-waste

**250**

134274.

[25] Myhre, G., Shindell, D., Breón, F.- M., Collins, W., Fuglestvedt, J., Huang, J., Koch, D., Lamarque, J.-F., Lee, D., Mendoza, B., Nakajima, T., Robock, A., Stephens, G., Takemura, T., Zhang, H. 2013. Antrhropogenic and natural radiative forcing. Chpt. 8, in: Stocker, T. F., Qin, D., Plattner, G.-K., Tignor, M., Allen, S.K., Boschung, J., Nauels, A., Xia, Y., Bex, V., Midgley, P.M. (eds), Climate Change 2013: The Physical Science Basis. Contribution of the Working Group I to the Fifth Assessment Report of the Intergovernmental Panel on Climate Changes, Cambridge University Press, Cambride, UK, and New York, NY, USA, www.ghghprotocol.org, 640–659.

[26] ESRL, 2019. Earth System Research Laboratory GMD (Global Monitoring Division), www.esrl.noaa.gov/mgd/dv/ iadv (accessed on 08.03.2019).

[27] Stockwell, C.E., Yokelson, R.J., Kreidenweis, S.M., Robinson, A.L., DeMott, P.J., Sullivan, R.C., Reardon, J., Ryan, K.C., Griffith, D.W.T., Stevens, L., 2014. Trace gas emissions from combustion of peat, crop residue, domestic biofuels, grasses, and other fuels: configuration and Fourier transform infrared (FTIR) component of the fourth Fire Lab at Missoula Experiment (FLAME-4). Atmospheric Chemistry and Physics, 14, 9727–9754.

[28] Yokelson, R.J., Bertschi, I.T., Christian, T.J., Hobbs, P.V., Ward, D.E., Hao, W.M., 2003. Trace gas measurements in nascent, aged, and cloud-processed smoke from African savanna fires by airborne Fourier transform infrared spectroscopy (AFTIR). Journal of Geophysical Researchm 108(D13), 8478.

[29] Wahrenberger, C.M., 1997. Some aspects of the chemistry of volcanic gases. Ph.D. thesis, Swiss Federal Institute of Technology, Zurich, Switzerland, 233 pp.

[30] Ali, G., 2004. Identification of volatile organic compounds produced by algae. Egyptian Journal of Phycology, 5, 71–81.

**Chapter 14**

**Abstract**

95 μg m�<sup>3</sup>

**1. Introduction**

**253**

of Delhi, India

*and Sanjeev Kumar Goyal*

Evaluation of Particulate Matter

*Saurabh Mendiratta, Sunil Gulia, Prachi Goyal*

PM2.5, and PM1 are found in the range of 55–150 μg m�<sup>3</sup>

respectively in Building II and 216–330 μg m�<sup>3</sup>

, respectively in Building I, 33–136 μg m�<sup>3</sup>

pattern, indoor sources, indoor/outdoor ratio, office buildings

Pollution in Micro-Environments

of Office Buildings—A Case Study

High level of particulate matter in an office building is one of the prime concerns for occupant's health and their work performance. The present study focuses on the evaluation of the distribution pattern of airborne particles in three office buildings in Delhi City. The study includes the Assessment of PM10, PM2.5 and PM1 in the different indoor environments, their particle size distribution, I/O ratio, a correlation between pollutants their sources and management practices. The features of buildings I, II, and III are old infrastructure, new modern infrastructure, and an old building with good maintenance. The results indicate that the average concentrations of PM10,

respectively in Building III. The maximum proportion of the total mass contributed by PM0.25–1.0 i.e., up to 75%, 86%, and 76% in the meeting room of Building I, II and III, respectively. The proportion of ultrafine particles was found higher in the office area where the movement was minimum and vice versa. The higher I/O indicates the contribution of the presence of indoor sources for ultra-fine and finer particles. Further, possible strategies for indoor air pollution control are also discussed.

**Keywords:** ultrafine particulate matter, size segregated particles, distribution

Indoor Air Quality (IAQ) refers to the level of air pollutants and thermal (temperature and relative humidity) conditions that affects the health, comfort, and performance of the occupants inside a building. The high concentration of air pollutants indoor is a major concern in Delhi city, which has been many times reported as one of the polluted cities of the world [1]. The major sources in an office building are infiltration of ambient air pollutants; emissions from office equipment like printers, xerox. Etc.; emission of VOCs from building materials, re-suspension of floor dust; emission from cleaning chemicals among them [2]. In addition to the sources, poor ventilation builds the pollutant level indoors [3]. The increasing level of pollutants

, 41–104 μg m�<sup>3</sup> and 37–

, 30–84 μg m�<sup>3</sup> and 28–73 μg m�<sup>3</sup>

, 188–268 μg m�<sup>3</sup> and 171–237 μg m�<sup>3</sup>

,

,

## **Chapter 14**
