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Fossil Fuel Fires: A Forgotten Factor of Air Quality

Written By

Łukasz Kruszewski

Submitted: 18 September 2020 Reviewed: 29 January 2021 Published: 18 February 2021

DOI: 10.5772/intechopen.96294

Environmental Sustainability IntechOpen
Environmental Sustainability Preparing for Tomorrow Edited by Syed Abdul Rehman Khan

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Environmental Sustainability - Preparing for Tomorrow

Edited by Syed Abdul Rehman Khan

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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.

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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 cross-sensitivity 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.

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 cryo-trapping) 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.).

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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 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 low-temperature supergene weathering processes ([6, 10, 11, 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, millosevichite-mikasaite solid solution, (Al,Fe)2(SO4)3, steklite, KAl(SO4)2, tschermigite, (NH4)Al(SO4)2·12H2O (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, 18, 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.%; CO267.2, 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; NO216430, 116, 24, 191; NH31715, 646, 14, 98; SO2582, 74, 64, 226; HCl 58, 23, 2.4, 8.9; CCl422, 1.5, 6.0, 14; HF 4.0, 2.2, n.o., 5.1; SiF4 1890, 228, 504, 1980; AsH38.2, 0.49, 0.18, 0.64; CH482970, 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 (ntotal = 46); CO2 31, 4.0, 0.22, 11, and 7.0 (ntotal = 50) [vol.%]; CO 84, 186, 9.6, 81, and 81 (ntotal = 41); NO 87, 15, 14, 66, and 42 (ntotal = 24); NO2 334, 38, 14, 42, and 41 (ntotal = 26); N2O -, 0.10, 0.66, 4.3, and 0.83 (ntotal = 17); NH3 287, 22, 3.4, 59, and 88 (ntotal = 18); SO2 110, 18, 17, 48, and 56 (ntotal = 31); HCl 7.4, 4.2, 0.56, 3.0, and 3.8 (ntotal = 46); CCl4 3.2, 0.18, 0.91, 2.5, and 1.6 (ntotal = 51); HF 4.0, 2.2, −, 3.3, and 3.4 (ntotal = 9); SiF4 16, 114, 94, 182, and 65 (ntotal = 29); AsH3 1.1, 0.19, 0.17, 1.0, and 0.58 (ntotal = 26); CH4 1945, 500, 23, 537, and 457 (ntotal = 47); ethane 46, 114, 15, 75, and 59 (ntotal = 37); propane 148, 70, 16, 27, and 46 (ntotal = 27); hexane 160, 25, −, 15, and 38 (ntotal = 26); ethene 7.9, 7.3, 11, 8.3, and 8.2 (ntotal = 28); DCM 230, 119, 160, 295, and 214 (ntotal = 45); 1,1-DCE 235, 190, 98, 99, and 139 (ntotal = 32); 1,2-DCE 153, 28, 7.4, −, and 91 (ntotal = 9); 1,1,1-TCE 5.4, −, 40, 9.5, and 7.7 (ntotal = 19); 1,2-DCP 1038, 5.7, −, 20, and 166 (ntotal = 9); 1,1-DCEe 19, 2.6, 31, 25, and 20 (ntotal = 35); vinyl chloride 329, 38, −, 394, and 289 (ntotal = 32); chlorobenzene 24, 36, 92, 32, and 32 (ntotal = 12); cumene 28, 30, 35, 15, and 22 (ntotal = 38); phenol 14, 36, 3.8, 32, and 19 (ntotal = 32); o-cresol 115, 21, −, 99, and 73 (ntotal = 15); furan 11, 9.8, 72, 12, and 31 (ntotal = 18); THF 126, 372, −, 643, and 195 (ntotal = 10); thiophene 251, 200, 90, 156, and 186 (ntotal = 40); formaldehyde 3.5, −, −, 0.54, and 0.82 (ntotal = 8); acetic acid 189, 6.6, 8.1, 83, and 54 (ntotal = 22); DMS 517, 433, −, 921, and 533 (ntotal = 16); DMDS 68, 11, −, 31, and 41 (ntotal = 35); and pyridine -, −, 11, −, and 11 (total 8 records).

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 semi-quantitative 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.

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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.

vent 1CLD1CLD1oCLD2CLD3CLD5CLD5SCLD5oCLD6oCLD6o2CLD7CLdACLdArCLdUCLdCL1CLdoCL2aCL2aA
T [oC]404545452535353535609090828250823045
pFTIR
inorganics, vol.%
H2O29.7712.2112.2212.2716.4317.3616.8817.6217.6518.122.682.652.572.580.752.626.107.30
CO21.962.322.342.401.902.262.082.392.542.850.030.030.030.03bdl0.0318.0027.00
inorganics, ppm
CObdlbdlbdlbdl1353101101132941036.43.1bdl0.98bdl1.5145163
N2O2.83.43.53.5bdlbdlbdlbdlbdl0.570.020.040.060.01bdl0.02bdlbdl
NO64107112112bdlbdlbdlbdlbdlbdl6.99.9bdl9.71.610bdlbdl
NO2bdlbdlbdlbdlbdlbdlbdlbdl1144bdlbdlbdlbdlbdlbdl36865
NH34.43.93.63.710152110119.4bdl1.00.231.4bdl1.41830
SO24.2bdlbdlbdlbdl87bdlbdl20120bdlbdlbdl1.9bdl2.4119671
HCl0.04bdl0.240.571110108.77.66.61.50.760.080.580.010.636.55.8
CCl4bdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdl6.6
HFbdlbdlbdlbdlbdl0.62bdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdl0.03
SiF4bdl0.060.210.163.75.33.83.46.34.62.21.91.92.11.12.12031
AsH3bdl0.080.170.150.03bdlbdlbdlbdlbdlbdlbdl0.16bdlbdlbdl0.201.7
aliphatic and aromatic hydrocarbons and their derivatives, ppm
CH4263131312442592622512532484.54.86.84.60.514.88112950
ethanebdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdl30bdl
propane6.93.84.44.4344236bdl4037bdl4.23.113118.2bdl729
hexane1.80.200.310.352.64.62.37.04.611bdlbdlbdlbdlbdlbdl15217
ethenebdlbdlbdlbdlbdl1.3bdlbdl3.76.62.2bdl1.3bdl1.9bdl3779
DCM1710161573104711415720526556501851368159
1,1-DCEbdlbdlbdlbdlbdlbdlbdl7.2bdlbdlbdl5.1bdl7.4bdl7.21712
1,2-DCEbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdl77bdl
ventCLD1CLD1oCLD2CLD3CLD5CLD5SCLD5oCLD6oCLD6o2CLD7CLdACLdArCLdUCLdCL1CLdoCL2aCL2aA
1,1,1-TCEbdlbdlbdlbdl99bdlbdlbdlbdl21bdlbdlbdl6.4bdl6.5417bdl
1,2-DCPbdlbdlbdlbdlbdlbdlbdl31bdlbdlbdlbdlbdlbdlbdlbdl56bdl
1,1-DCEe4.35.34.44.8577754634368354549482557226347
ClBbdlbdlbdlbdl20bdl1839bdlbdl1514226.06.06.3bdl186
cumene4.46.36.45.52930312934316.11.37.61.92.41.7399bdl
phenol2.44.44.24.029bdl292817174.63.27.0bdl2.9bdlbdlbdl
o-cresole0.29bdl0.410.371946172023241.92.20.287.10.816.96610
heterocyclic organic compounds, ppm
furanbdl0.14bdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdl
THF0.29bdl1.30.18bdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdl177
pybdlbdlbdlbdlbdl7.1bdlbdlbdlbdl0.272.36.312231286bdl
tphbdlbdlbdlbdl192137191bdl127103bdlbdlbdlbdl8.3bdlbdl173
other organic compounds, ppm
fm0.11bdlbdlbdl127.06.05.35.35.70.581.20.470.420.450.421313
DMSbdl137.711626.927333151bdl0.15bdlbdlbdlbdl893165
DMDS)1223322899104407.0855.63.53731361736bdlbdl
GC – additional compounds, ppm
ventCLD1CLD1oCLD2CLD34CLD5CLD5SCLD5oCLD6oCLD6o2CLD7CLdACLdArCLdUCLdCL1CLdoCL2aCL2aA
CH3Cl0.0020.0010.0030.0020.0050.0020.080.030.01
ethyne0.0010.0010.0010.0010.010.0030.010.010.0002
propene0.0002bdl1.75.21.40.090.510.360.09
i-butane0.00030.0021.63.23.50.080.698.32.3
n-butane0.0010.0022.45.43.60.151.1123.9
1-butene0.00010.0010.140.400.130.020.030.080.03
i-butene0.00010.0020.410.320.520.030.041.30.42
t−2-bu0.000040.0010.521.40.500.020.040.590.24
c-2-bu0.000030.00050.290.800.230.010.020.170.06
ventCLD1CLD1oCLD2CLD3CLD5CLD5SCLD5oCLD6oCLD6o2CLD7CLdACLdArCLdUCLdCL1CLdoCL2aCL2aA
i-pentane0.0010.010.921.81.80.060.356.51.7
n-pentane0.00030.011.12.31.50.060.356.01.9
t-2-ptebdl0.0020.200.570.190.010.010.360.18
c-2-ptebdl0.0010.080.230.070.0040.0030.090.04
n-heptanebdl0.0030.440.840.340.020.071.70.68
n-octanebdl0.0020.360.650.100.010.040.640.32
n-nonanebdl0.00030.250.400.030.010.010.220.04
n-decanebdl0.00010.160.200.0030.0010.0020.030.04
2,3-DMBubdl0.010.070.130.160.0030.020.580.14
2-MPTbdl0.010.410.760.750.020.113.00.82
ventCLD1CLD1oCLD2CLD3CLD5CLD5SCLD5oCLD6oCLD6o2CLD7CLdACLdArCLdUCLdCL1CLdoCL2aCL2aA
3-MPT0.00010.0050.160.300.300.010.051.30.34
cptbdl0.0010.190.420.260.010.051.00.30
benzene0.00040.0022.13.30.060.050.271.10.41
toluene0.0010.022.03.40.010.020.110.050.02
EtB0.00010.0030.270.430.010.010.020.120.05
m/p-X0.00030.011.31.90.190.020.090.060.22
o-X0.00020.0030.390.530.030.010.030.020.01
styrene0.0010.0001bdlbdlbdlbdlbdlbdlbdl
i-PrBbdl0.00020.030.050.030.0010.0010.060.03
n-PrBbdl0.00050.060.080.020.0010.0020.020.01
m-EtT0.00010.0010.180.240.060.0040.010.010.01
p-EtTbdl0.00050.070.100.020.0010.0030.010.01
o-EtTbdl0.00050.080.100.020.0030.0020.010.01
1,3,5-TMB0.00010.0010.140.190.070.0030.0050.010.005
1,2,4-TMB0.00010.0020.270.320.050.010.010.040.03
1,2,3-TMB0.00010.0010.100.100.020.0040.0030.060.05

Table 1.

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

“A” – samples taken from the depth of 0.8–1 m; “a” and “o” - nearby vents; “r” – repeated analysis; “S” – sulfur-mineralized vent.


DCM – dichloromethane, DCE – dichloroethane, DCEe – dichloroethene, TCE – trichloroethane, DCP – dichloropropane, ClB – chlorobenzene, THF – tetrahydrofuran, py – pyridine, tph – thiophene, fm – 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.


Notable (>100 ppm) enrichment given in bold.


GC data for a nearby vent.


Values in parentheses denote overrun of the upper measurement range.

vent1RD07RD07ARD08NRD08NARD08krRD08krARD08oRD11LRD11URD11oBTM1BTM1ABTM1oBTM1o2BTM1o3BTM1o4BTM2
T [oC]60901331877710776767676115144731507911560
pFTIR
main components, vol. %
H2O219.9924.6226.0218.2627.1422.2526.6116.9424.8026.656.929.9410.4110.6711.1511.029.43
CO225.0029.8920.2113.9426.1621.3221.2411.9621.1424.644.085.435.525.257.588.127.49
inorganics, ppm
CO158024309235021110813832673103011001730283030902640309035902210
N2Obdlbdlbdlbdlbdlbdlbdl4.4bdlbdlbdlbdlbdlbdlbdlbdl2.8
NObdlbdlbdlbdlbdlbdl7.3bdlbdlbdlbdlbdlbdlbdlbdlbdlbdl
NO2bdl2.0bdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdl1430bdlbdl
NH39.29.25.56.912195.01.83.11642606061626541
SO2388311bdl57bdl193bdl79bdlbdl86139147139532378281
HCl4.53.16.12.92.52.66.2bdl5.02.32.73.33.65.419156.3
CCl46.35.1104.46.86.93.27.4117.8bdlbdlbdlbdl1.1bdlbdl
HF0.12bdlbdlbdlbdlbdlbdlbdlbdlbdlbdl0.590.071.1bdlbdlbdl
SiF4151321161515181714131.71.81.70.95bdl3.2bdl
AsH3bdl1.30.930.491.21.40.561.7bdl0.110.812.91.32.00.792.83.4
aliphatic and aromatic hydrocarbons and their derivatives, ppm
methane31903470112071311201160114050011201150285437421359808819554
ethanebdl142bdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdl281bdlbdl
propane387601202bdl291230213bdl195249bdlbdlbdlbdl694242bdl
hexane71139705390677153647688148160309608543138
ethenebdl0.71125.49.37.612123.16.94.7161739847835
DCM8.3181262910425111941023411687484bdlbdlbdl
1,1-DCEbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdl16bdlbdlbdl
1,2-DCE39bdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdl38bdlbdlbdl
ventRD07RD07ARD08NRD08NARD08krRD08krARD08oRD11LRD11URD11oBTM1BTM1ABTM1oBTM1o2BTM1o3BTM1o4BTM2
1,1,1-TCE291521332936bdl21bdlbdlbdlbdl1.0bdl59bdl20
1,2-DCP1243847542264175224108251248bdlbdl39bdl568bdl519
1,1-DCEe8130195101164123176155189162bdl1111bdl2428bdl
ViCl41696276187248283269bdl20327838294763137205359
ClBbdlbdlbdlbdl11bdl74bdl776262466111273206bdl
cumene941261193610110812310511490384650264117bdl107
phenolbdl1549bdl211.651bdl111718394247606735
o-cresole3765254034502639303127464853817376
heterocyclic organic compounds, ppm
THF4396bdl3.1bdl9.38.74.16.112bdlbdlbdl232bdlbdl293
tph16425733738536336934430155639163bdlbdlbdl689201388
other organic compounds, ppm
fmbdlbdl2.61.42.02.05.51.41.31.60.740.770.911.217172.1
acacbdl9.1bdlbdlbdlbdlbdlbdlbdlbdlbdlbdl2.2bdl359.950
DMS13112647401bdl16702552715172219243154013701200bdl
GC – additional compounds,ppm
ventRD07RD07ARD08NRD08NARD08krRD08krARD08oRD11LRD11URD11oBTM1BTM1ABTM1oBTM1o2BTM1o3BTM1o4BTM2
CH3Cl0.0010.051.40.030.030.020.010.100.02
COS7.40.782.60.880.162.10.431.30.98
ethyne0.010.010.0010.0030.0030.0020.040.0020.004
propene0.470.910.930.010.033.81.58.50.62
i-butane3.31.70.080.0050.132.02.62.41.7
n-butane8.73.60.210.010.034.63.45.92.6
1-butene0.010.020.130.0030.0050.240.131.60.05
i-butene0.060.080.510.0020.010.980.386.60.26
t-2-bu0.010.060.160.0010.010.780.242.30.07
c-2-bu0.010.030.120.00050.0030.470.181.60.04
i-pentane2.00.770.040.0040.091.21.11.20.80
ventRD07RD07ARD08NRD08NARD08krRD08krARD08oRD11LRD11URD11oBTM1BTM1ABTM1oBTM1o2BTM1o3BTM1o4BTM2
n-pentane3.31.10.070.0050.062.11.21.70.91
isoprenebdl0.0020.030.00030.0010.020.010.130.003
1,3-budibdlbdl0.020.0002bdlbdlbdl0.03bdl
t-2-pte0.120.010.060.0010.010.210.080.810.01
c-2-pte0.050.0030.030.00040.0020.090.030.390.003
n-heptane0.440.180.030.0010.010.580.410.930.11
n-octane0.050.050.030.00070.0040.180.210.570.05
n-nonane0.030.460.020.00030.0010.080.150.440.10
n-decane0.0030.020.010.00010.00020.020.110.600.01
2,3-DMB0.120.040.0030.00020.0040.090.080.080.06
2-MPT0.640.220.010.0010.020.530.430.330.28
3-MPT0.260.100.020.0010.0010.220.170.110.17
cpt0.700.250.010.00040.0030.400.270.220.20
benzene5.33.24.30.130.465.533211.3
toluene0.160.270.660.0050.131.60.537.60.27
EtB0.010.080.080.00030.020.090.103.60.06
m/p-X0.030.110.280.0010.050.340.363.00.17
o-X0.010.050.130.00040.010.180.151.10.07
styrene0.0010.010.0050.000030.0010.010.010.140.003
i-PrB0.0010.020.01bdl0.0010.0030.020.710.01
n-PrB0.0020.010.040.00010.0020.0030.020.270.01
m-EtT0.010.050.110.000100030.010.080.540.05
p-EtT0.0020.020.050.000030.0010.010.060.380.02
o-EtT0.0040.020.040.000050.0010.010.050.250.02
1,3,5-TMB0.010.020.050.00010.0010.010.110.380.02
1,2,4-TMB0.010.080.170.00010.0030.020.131.00.05
1,2,3-TMB0.010.050.070.00010.0010.010.140.550.04

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).

the “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” – pyrometamorphic zone, “S” – sulfur-mineralized vent.


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


Notable (>100 ppm) enrichment given in bold.


Values in parentheses denote overrun of the upper measurement range.

vent 1SWC1SWC1rSWC1oPSWC1oSWSWC1oBSWC2SWC2oSWC2o2SWC2o3SWC3SWC3ARCH1RCH1AZBB1ZBB1AZBB2ZBB2oZBB3
T [oC]45451001004518018065654330030491502108686100
pFTIR
main components, vol. %
H2O22.473.914.384.293.986.426.376.246.374.434.507.287.8125.6322.5625.5321.5221.13
CO2bdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdl0.110.7938.3133.9534.7525.7738.41
inorganics, ppm
CO921431661641441090107010601040172176212112201260093895226700
N2Obdlbdlbdlbdlbdl1.31.31.31.2bdlbdlbdl2.6bdlbdlbdlbdlbdl
NO1215bdlbdl19bdlbdlbdlbdlbdlbdl100bdlbdlbdlbdlbdlbdl
NO2bdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdl66bdlbdl31
NH31.53.14.13.13.0bdlbdlbdlbdl2.01.412bdl8.3bdlbdlbdl8.3
SO2bdl1546bdl14795958533947129172bdlbdlbdl123bdl
HCl0.480.732.92.70.948.48.38.38.33.73.90.711.24.31.25.65.94.9
CCl40.570.030.06bdl0.11bdlbdlbdlbdl0.340.34bdlbdl6.08.58.58.24.0
HF0.19bdlbdl1.1bdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdl
SiF4bdl0.082.42.50.18484847473.03.50.42bdl2515282610
AsH30.040.090.40bdl0.28bdlbdlbdlbdl0.380.37bdlbdl0.882.90.19bdl2.9
aliphatic and aromatic hydrocarbons and their derivatives, ppm
methanebdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdl9.812111074011301130880
propane19272bdlbdl85343737392082151112233bdl257277bdl
hexanebdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdl3869394064
ethenebdlbdlbdl2.3bdl2626248.5bdlbdlbdlbdl1819212321
DCM3019112820181191191189363917314392142467682
1,1-DCE12bdlbdlbdlbdl103102102104bdlbdl112.4bdlbdlbdlbdlbdl
1,2-DCEbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdl59bdlbdl60
1,1,1-TCEbdlbdl1.8bdlbdl492447444436bdlbdl63bdl23bdl2665bdl
ventSWC1SWC1rSWC1oPSWC1oSWSWC1oBSWC2SWC2oSWC2o2SWC2o3SWC3SWC3ARCH1RCH1AZBB1ZBB1AZBB2ZBB2oZBB3
1,2-DCPbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdl546761bdl214114bdl
1,1-DCEe7.2bdl2721bdl287274272272303320622116613019117656
VCbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdl32314536529997
ClB9.5bdlbdl51bdl192239248.37.7bdl24bdl73bdlbdl67
cumenebdlbdlbdlbdlbdl66646250bdlbdl4239901612892153
phenol4.9bdl0.459.7bdlbdlbdlbdlbdlbdlbdlbdlbdl201134bdl36
o-cresole2.41.65.62.51.4131312136.27.156523022396316
heterocyclic organic compounds, ppm
THFbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdl36bdl3221bdl
py17820219168206bdlbdlbdlbdl231232bdlbdlbdlbdlbdlbdlbdl
tphbdl14626bdl149260204200194151141bdlbdl496bdl448282bdl
other organic compounds, ppm
fm1.80.217.15.70.317.47.57.59.42.83.11.61.9bdl1.22.8bdl2.2
DMSbdlbdlbdlbdlbdlbdlbdlbdlbdlbdlbdl23176515360148120
DMDS380289bdl16293bdlbdlbdlbdl3223217.112bdlbdlbdlbdlbdl
GC – additional compounds
ventSWC1SWC1rSWC1oPSWC1oSWSWC1oBSWC2SWC2oSWC2o2SWC2o3SWC3SWC3ARCH1RCH1AZBB1ZBB1AZBB2ZBB2oZBB3
CH3Cl0.0010.060.010.040.0010.0012.00.21
COS0.0030.012.10.45
ethyne0.0010.00040.020.240.00010.0040.020.02
propenebdl0.010.651.60.0010.0011.60.03
i-butane0.0020.0010.150.060.010.030.530.03
n-butane0.0040.0020.550.270.010.132.00.07
1-butenebdl0.0010.050.180.00020.00020.170.02
i-butenebdl0.0020.090.370.00030.00050.240.01
t-2-bu0.0010.0010.090.200.00010.00030.280.02
c-2-bu0.0010.0010.060.140.00010.00010.160.01
i-pentane0.0030.0010.100.04
ventSWC1SWC1rSWC1oPSWC1oSWSWC1oBSWC2SWC2oSWC2o2SWC2o3SWC3SWC3ARCH1RCH1AZBB1ZBB1AZBB2ZBB2oZBB3
i-pentane0.0030.0010.100.040.0020.010.340.01
n-pentane0.0020.0010.290.140.0050.030.960.03
isoprenebdlbdl0.003bdl0.0010.000050.010.001
1,3-budibdl0.00010.010.04bdlbdlbdl0.01
t-2-pte0.00020.00040.040.040.00020.0010.090.01
c-2-pte0.00010.00030.020.020.00010.00020.040.002
n-heptane0.0010.0010.120.070.0010.010.330.01
n-octane0.00020.0010.100.050.00010.0010.180.004
n-nonane0.00030.00030.080.030.000040.0010.070.003
n-decane0.00030.00030.060.020.000040.0010.040.0002
2,3-DMBu0.02bdl0.01bdl0.00010.0010.020.001
2-MPT0.260.0010.050.030.0010.0040.150.003
3-MPT9.90.00020.020.010.00030.0010.070.001
cpt0.00050.00020.040.010.00050.0030.100.002
benzene0.00010.030.501.70.0030.461233
toluene0.010.0050.220.410.0020.0022.70.01
EtB0.00040.0010.030.040.0010.0010.090.004
m/p-X0.0010.0020.070.150.0020.0020.340.01
o-X0.0010.0010.030.060.0010.0010.130.005
styrenebdlbdl0.003bdl0.000020.00030.020.0004
i-PrB0.0002bdl0.0020.0040.000020.00020.0030.001
n-PrB0.00040.00040.010.010.00010.00030.020.001
m-EtT0.0010.00020.010.020.00030.0010.040.003
p-EtT0.00040.00010.0040.010.00010.0010.020.001
o-EtT0.00020.00010.010.010.00010.00040.020.001
1,3,5-TMB0.001bdl0.010.010.00010.00040.010.001
1,2,4-TMB0.0010.00040.020.030.00050.0010.050.01
1,2,3-TMB0.00040.00020.010.010.00020.0010.030.004

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).

The “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” – pyrometamorphic zone, “S” – sulfur-mineralized vent.


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


Notable (>100 ppm) enrichment given in bold.


Values in parentheses denote overrun of the upper measurement range.

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, 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.

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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.

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.

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′]-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.

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Acknowledgments

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

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Written By

Łukasz Kruszewski

Submitted: 18 September 2020 Reviewed: 29 January 2021 Published: 18 February 2021

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

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