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Polycyclic aromatic hydrocarbons in particulate matter emitted from coke oven battery
Fuel 144 (2015) 327–334
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Polycyclic aromatic hydrocarbons in particulate matter emitted from coke oven battery Barbara Kozielska a,⇑, Jan Konieczyn´ski b a b
Silesian University of Technology, Faculty of Power and Environmental Engineering, Department of Air Protection, 2 Akademicka St., 44-101 Gliwice, Poland Institute of Environmental Engineering, Polish Academy of Sciences, 34 M. Skłodowskiej-Curie St., 41-819 Zabrze, Poland
h i g h l i g h t s
g r a p h i c a l a b s t r a c t
Determination of 13 PAHs in dust
Average percentage of individual PAHs in total PAHs bounded with TSP of the coke oven battery sampling zones.
captured in a close neighborhood of coke oven battery has been done. Characteristic for coking process ratios of selected pairs as well as PAH’s profiles in TSP were determined. Investigation was carried out on a plant fulfilling all BAT requirements. PAHs analyzes were done with use of gas chromatography techniques.
a r t i c l e
i n f o
Article history: Received 21 October 2011 Received in revised form 16 December 2014 Accepted 17 December 2014 Available online 29 December 2014 Keywords: Air pollutants TSP PAH Diagnostic ratios Poland
a b s t r a c t Coke oven battery is one of the main sources of fugitive total suspend particles (TSP) and polycyclic aromatic hydrocarbons (PAHs) in coke plants. In this study the content of selected PAHs associated with the TSP in the immediate vicinity of the coke oven battery Radlin (Poland) was investigated. TSP collection places were located on battery wall, battery roof, pusher machine and coal transfer car. Revealed TSP concentrations were within the range of 0.50–5.15 mg/m3, the total content of PAHs within wide range of 216.6–28018.9 lg/g. Regardless of the concentration level of PAHs connected with the TSP in the coke oven battery surrounding, it was found that four rings PAHs are the main fraction (50–70%). The high average concentrations of benzo[a]pyrene (BaP) and Toxicity Equivalent BaP (BaPeq) reaching 1.29 and 2.63 lg/m3 respectively in the immediate vicinity of coke oven battery, could pose a serious threat to the health of a coking plant workers. Calculated diagnostic ratios BaA/(BaA + Ch), Fl/(Fl + Py), BaP/ (BaP + Ch), BbF/BkF, BaP/BghiP, BaA/Ch are characteristic for the coking process. Ó 2014 Elsevier Ltd. All rights reserved.
1. Introduction
⇑ Corresponding author. Fax: +48 32 237 12 90. E-mail address: [email protected] (B. Kozielska). http://dx.doi.org/10.1016/j.fuel.2014.12.069 0016-2361/Ó 2014 Elsevier Ltd. All rights reserved.
Coke production is found to be the crucial environmental nuisance. This is caused by the fact, that it is not possible to make such process fully hermetic.
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The greatest total dust and gases emission source in the coking industry is the coke oven battery. Among emitted pollutants polycyclic aromatic hydrocarbons (PAHs) are present. The recent interest in emission of PAHs from national coke industry is caused by its high production potential (10 mln Mg/a) which results in its significant share in PAHs emission established at the level of 20 Mg/a, including benzo[a]pyrene – 8 Mg/a. It must be emphasized that, polish coke plants meet all the requirements of European emission standards. The determination of the coke plant impact on the environment mostly is done using emission factors. The estimated emission factors for total PAHs as well as for individual ones are different depending on place and measurement procedures e.g. in studies carried out in 1978–1989 by Bjorseth, Eisenhut, Tonelaar and Duiser the total PAHs emission factors were in range of 2.5– 15 g/Mg [1–4]. Despite significant differences in values some similarities also can be found. One is the concentration of particular PAHs group, which is the greatest for lighter, 3–4 rings PAHs (from 74 to 84 wt.%), and then for 5–6 rings PAHs (from 16 to 26 wt.%). It is also found that among 3-ring PAHs share of phenanthrene is very high and reaches up to 45.9% [5]. Further studies carried out by Bendrowski in 1995 allowed to established obligatory emission factors of benzo[a]pyrene, benzo[b]fluoranthene, benzo[k]fluoranthene and indeno[1,2,3–cd]pyrene as both, single compounds and their sum – R4 PAHs [6]. The determination of qualitative and quantitative composition of PAHs emitted from a given technological process and their appearance in gaseous and solid phases enables to specify PAHs emission source. In case of coke industry, profiles of PAH groups differ in number of rings in the particle or characteristic PAHs ratios (values of mass ratios of individual PAHs and PAH groups present in the dust) and thus are convenient to establish coke oven battery fingerprints and tracers. According to Khalili 89.8% share of naphthalene and 9.4% share of 3-ring PAHs in total amount of 20 determined PAHs can be stated as fingerprint of coke plant [7]. Fluorene present in the air is one of the coke plant tracers [8]. Harrison et al. found that common appearance of particular PAHs was the emission source marker. Hence, chrysene and benzo[k]fluoranthene are coal combustion markers, coronene and phenanthrene are combustion engines emission markers, pyrene, fluoranthene and phenanthrene are waste incineration plant markers, while heating oil combustion results in emission of fluorene, fluoranthene and pyrene together with benzo[b]fluoranthene and indeno[1,2,3-cd]pyrene [9]. In order to determine the share of emission source in PAHs concentration in air, the comparison of PAHs profiles mainly presented in TSP is made [10,11]. Comparing the results obtained in Belgium [12] it was found that ambient air close to steelworks contained anthracene, pyrene, benzo[g,h,i]perylene and chrysene what could be caused by emission from coke oven batteries. Analyses and measurements of PAHs concentration in both, gaseous and solid phases of air samples collected 100 m away from coke oven battery revealed that profiles of PAHs in ambient air significantly depended on wind direction and presence of other sources [13]. PAHs ratios in atmospheric particles have different values depending on emission source. The analysis of coke plant dust performed by Khalili and Simcik revealed characteristic, higher than 5 ratio of BaP/BghiP, 0.79 ratio of Ph/An, 0.7 ratio of BaA/Ch and 2.5 ratio of BeP/BaP [7,8]. In this case values of BaP/ BgP or Py/BaP ratios, indicated cars with combustion engines as the main emission source [14–16]. PAHs appear in either gaseous or solid phases or in both of them. Distribution of PAHs between gas and solid phase depends on environmental conditions i.e. ambient temperature, air humidity, particles concentration and PAHs properties i.e. molecular weight, vapor pressure, particles size, surface area and the nature of particulate [17–20], photochemical degradation and radical reactions [21,22]. Airborne PAHs with less than three aromatic
rings (mol wt. 128–178) are gaseous, whereas PAHs with five or more rings (mol wt. >228) occur in the solid phase [23–25]. Lee et al. established the level of PAHs bound to airborne particulates in ambient air around the traffic source in the range 28.3–67.3% (46.1% in average). Simultaneously, the mean particle phase distribution of total PAHs in the urban and rural atmospheres was only 18.7% and 20.6%, respectively [17]. Ravindra et al. indicated that concentration of PAHs in gaseous phase was 10 times higher than in particles of dust present in analyzed samples. However, the share of PAHs stated as hazardous reaches ca. 55% in solid phase, while in gaseous phase it is only 2% [12]. 2. Experimental The study was based on a modern coke oven battery in Radlin Coke Plant fulfilling best available technique (BAT) requirements, and it comprises determination of PAHs concentration in TSP in direct proximity to coke oven battery, investigation of PAHs profiles and characterization of their composition to indicate emission source markers. The battery was built in 2009, it contains 2 blocks which comprise 43 coking chambers of dimensions (mm) 15900 5000 500 each, its coke production capacity reaches 750 thousand Mg/a. The charging of chambers is done using stamp method, while coke quenching by means of wet method. The pneumatic sealing of ascension pipes closure is applied. For limitation of pollutants emissions during chambers discharging coke transfer machine is equipped with integrated suction hood followed by dedusting installation. The dedusting process is carried out in 2 devices arranged in series i.e. cyclone and bag filter [26]. Points, where air polluted with gases and dust emitted from the battery in unorganized manner were sampled, had been determined considering different phases and conditions of coking process. TSP samples were collected in the nearest surrounding of coke oven battery (Fig. 1). This manner of samples collection reduces the possible PAHs transformations, caused by chemical reactions i.e. oxidation, phototransformation and interaction with other compounds as well as influence of others PAHs sources to minimum. TSP samples were collected on 17th and 18th of September 2009 by StaplexÒ TFIA Series High Volume Air Samplers (The StaplexÒ Company, New York, USA). Sampler was equipped with SH 810 Filter Holder Assemblies. During the measurements, the weather conditions were as follows: temperature 15–16 °C, absence of rain, wind velocity below 3 m/s and pressure 973 hPa. The mass of the sampled dust was determined gravimetrically (Sartorius balance, resolution 0.01 g). Before each weighing, the filters were conditioned for at least 48 h at the air temperature of 20 ± 1 °C and air relative humidity of 50 ± 5% in the weighing room. The sampling was carried out for 1 h, the volumetric air flow was greater than 50 dm3/min and the volume of collected air reached about 3.5 m3. 2.1. Sample preparation and analysis of PAHs Samples of TSP was extracted from filters in ultrasonic bath with dichloromethane (CH2Cl2). The extract was percolated, washed and dried in helium atmosphere. The dry residue was diluted in propanol-2 (CH3CH(OH)CH3) and next distilled water was added to receive alcohol/water volume ratio 15/85. For selective purification, the obtained samples were solidified (SPE) via extraction in columns filled with octadecylsilane – C-18, (Supelclear™ ENVI-18 Tubes, Supelco USA). PAHs were eluted with the use of dichloromethane. The extract of PAHs was thickened by helium atmosphere to volume of 0.5 cm3. A Perkin Elmer Clarus 500 gas chromatograph equipped with a flame ionization detector (FID) was used. An RTX-5 (Restek)
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CS - battery wall – coke side; PS - battery wall – pusher side; RCS - battery roof – coke side; RPS - battery roof – pusher side; CTC - coal transfer car; PuM - pusher machine Fig. 1. Sampling places of TSP at coke oven battery in Radlin Coke Plant.
capillary column 30 m 0.32 mm 0.25 lm, with non-polar stationary phase was applied to separate sample components. The flow of carrier gas i.e. helium was equal to 1.5 cm3/min. The samples were introduced into split/splitless injector. Temperatures of the injector and detector were 240 °C and 280 °C respectively. The initial temperature of the GC oven was 60 °C which was held for 4 min, next it was increased by 10 °C/min until it reached 280 °C, then it was held constant for 14 min. The total time of the analysis was 40 min. The detector was provided with hydrogen (45 cm3/min) and air (450 cm3/min). 13 of 16 USEPA priority PAHs were analyzed – list of PAHs and suitable abbreviations are shown in Table 1. The quantitative analysis was done basing on the calibration curves prepared for 16 standard PAHs (Na, Acy, Ace, F, Ph, An, Fl, Py, BaA, Ch, BbF, BkF, BaP, DBA, BghiP, IP). The linear correlation between the peak surface areas and the PAH concentrations was checked within the range 10–40 ng/ll (correlation coefficients 0.99, PAH Mix PM-611 Ultra Scientific standard of the concentration 100 lg/ml of each PAH was used). The analysis of each sample-series was accompanied with the analysis of a blank sample. The correctness of the applied method was checked by the analysis of the NIST SRM 1649b reference material and comparison of the results with the certified concentrations of the investigated PAHs (analyses of three certified samples of dust, 0.2 g each). The standard recovery was from 92% to 111%.
3. Results and discussion During the sampling of TSP present in the air, its concentration referred to one hour measurement was determined. Obtained
values are in the vast range of 0.50–5.15 mg/m3. The highest concentration was obtained for coke transfer car, next one for the battery roof – coke side and pusher machine. The lowest value was measured at coke side. The overall concentration of dust was stated as moderate. Mean concentrations of TSP in sampling zones were shown in Fig. 2. Similar results were obtained by Mu et al. [27]. In four typical coke plants in China at the top of coke oven, they found TSP levels in the range of 1.48–3.45 mg/m3. It was found [28] that in a total mass of PM10 there is 2.98% R9 PAHs in coking plant ‘‘Jadwiga’’ in Zabrze, 0.64% R9 PAHs in coking plant ‘‘De˛bien´sko’’ in Czerwionka-Leszczyny and 2.77% coking
Table 1 List of PAHs and abbreviations used in the text. Compound
Chemical formula
Abbreviation
Molar mass (g/mol)
Naphthalene Acenaphtene Acenaphthylene Fluorene Phenanthrene Anthracene Fluoranthene Pyrene Benzo[a]anthracene Chrysene Benzo[b]fluoranthene Benzo[k]fluoranthene Benzo[a]pyrene Dibenzo[a,h]antracene Benzo[g,h,i]perylene Indeno[1,2,3-cd]pyrene
C10H8 C12H10 C12H8 C13H10 C14H10 C14H10 C16H10 C16H10 C18H22 C18H22 C20H12 C20H12 C20H12 C22H14 C22H12 C22H12
Na Acy Ace F Ph An Fl Py BaA Ch BbF BkF BaP DBA BghiP IP
128.17 154.21 152.20 166.22 178.23 178.23 202.25 202.25 228.29 228.29 252.31 252.31 252.31 278.35 276.33 276.33
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I – standard deviation Fig. 2. The average concentration of TSP in the coke oven battery sampling zones and content of 13 PAHs in TSP.
´ ski / Fuel 144 (2015) 327–334 B. Kozielska, J. Konieczyn Table 2 The average summary content of 13 PAHs and 4 PAHs in TSP, Toxicity Equivalent BaP (BaPeq) in ambient air in the coke oven battery sampling zones.
Battery wall – pusher side (PS) Battery wall – coke side (CS) Battery roof – pusher side (RPS) Battery roof – coke side (RCS) Pusher machine (PuM) Coal transfer car (CTC) a
R13 PAH
R4PAHa
(lg/g)
(lg/g)
BaPeq (ng/m3)
2697.0 15654.0 11512.3 15914.3 1323.4 14787.2
928.7 6549.1 4649.9 6298.1 558.5 5815.5
793.7 2117.9 2661.5 5960.3 444.3 1617.9
BaP + BbF + BkF + IP.
plant ‘‘Radlin’’ in Radlin. For presented work the mean percentage of the R13 PAHs in TSP is 1.07%. In the presented work the R13 PAHs percentage in TSP in sampling points remains in the range of 216.7–28018.9 lg/g. The values of the R4 PAHs (BaP, BbF, BkF, IP) used in the coke industry in general assessing the impact of coking on the environment [6], ranges from 108.1 to 11522.8 lg/g. They represent 24.50–53.07% of total PAHs (40.61% in average) – Table 2. Ambient concentration of R13 PAHs (g/m3) ranges from 0.66 to 1.36 for battery wall – pusher side, 9.11–14.09 for battery wall – coke side, 1.21–30.22 for battery roof – pusher side, 13.69–41.32 for battery roof – coke side, 1.48–2.99 for pusher machine and 1.12–14.06 for coal transfer car. Liberti et al., carried out environmental monitoring at cokeoven batteries at the Taranto (Italy). They found R17 PAHs concentration (gaseous and particulate phases) for top-pusher machine side, top-coke side, pusher machine and pusher machine side 628 lg/m3, 426 lg/m3, 274 lg/m3, 329 lg/m3, respectively [29]. In turn Mu et al. in ambient air on the top of coke ovens stated concentration of R16 PAHs were contained in a range of 1.58– 146.98 lg/m3 [27]. In a gaseous phase the greatest share belongs to two rings (>93.3%) and three rings (87.4%) PAHs (Na, Acy, Ace, F, Ph, An) while in TSP five (92.3%) and six rings (99.1%) PAHs (BbF, BkF, BaP DBA, BghiP, IP). Four rings PAHs might appear in both gaseous phase and particle bound [30]. Among investigated compounds BaP is of a great interest considering its well known carcinogenic and mutagenic properties. The concentration of BaP in TSP sampled in coke oven battery zones was in the range of 6.7–3355.9 lg/g. The lowest value was obtained for battery wall – pusher side (PS2), while the greatest one for coal transfer car (CTC1). The concentration of BaP in ambient air was in the wide range of 109.99 ng/m3 for coal transfer car
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(CTC2), up to 4467.80 ng/m3 for battery roof – coke side (RCS1). The exception was the one measuring point on battery wall – pusher side (PS2), where the concentration 8.12 ng/m3 of BaP was relatively low. Ambient concentrations of TSP-related BaP in the neighborhood of the coke oven battery are alarmingly high and close to the extremely high concentrations of BaP found in the road tunnel in Nanjing (China) (2377 ng/m3 and 2534 ng/m3 in summer and winter, respectively) [31]. For comparison, concentrations of TSP-related BaP next to roadway in Katowice and Sosnowiec (Poland) were 10.82 ng/m3, and 9.91 ng/m3 respectively [32], while in Agra (India) in industrial-cum-residential it was 140 ng/ m3 [33]. Toxicity Equivalent BaP (BaPeq) was in the range of 169.96 ng/ m3 (coal transfer car – CTC2) to 11390.96 ng/m3 (battery roof – coke side – RCS1) with exception of battery wall – pusher side (PS2), where BaPeq was 32.69 ng/m3. In Table 2 average values of BaPeq in particular sampling zones are presented. Revealed BaPeq values are very high. Similar results were obtained by Mu et al. on the top of coke oven – 3140 ng/m3 [27]. Very high concentrations of BaP and BaPeq create health hazard for plant workers. For comparison, the BaPeq in the cities of Upper Silesia were: in winter 2007 in Zabrze for PM2.5–41.72 ng/m3, PM10–41.91 ng/m3 [34], in the heating season 2007/2008 PM2.5–31.70 ng/m3, PM10– 31.81 ng/m3 [35]. In Katowice (2009–2010) BaPeq concentration in PM2.5 for urban traffic was 2.88–474.24 ng/m3, while for the urban background 0.95–195.86 ng/m3 [36]. These values are much higher than for example in Xiamen: 0.85 ng/m3 and 0.92 ng/m3 for PM10 and PM2.5 bound PAH [37] or Shanghai – 15.77 ng/m3 [38]. Focusing on PAHs contained in the TSP is fully reasonable. Although PAHs in ambient air occurs mainly in a gaseous phase, the parts of them creating the highest hazard to human’s health appear mostly as bounded with TSP. For instance, Hassan and Khoder found that samples collected in summer and winter in an urban area in Dokki (Giza, Egypt) contain only 22.58% and 36.97% PAHs in TSP respectively. However, PAHs in the particulate phase pose higher potential health risk because the mean relative contributions of the total carcinogenic activity (concentrations) of all PAHs to the total concentrations of PAHs were 29.37% and 25.15% in the particulate phase and 0.76% and 0.92% in the gaseous phase during the summer and winter [39]. Very wide range of concentrations of PAHs in the studied samples of dust collected from the ambient air around battery results from its design and operation. It is worth mentioning that this is the installation consisting of dozens of reactors with reduced leakage, which run analogous processes, but in a different phase. Each phase of the process is characterized by intensity and composition of manufactured gas and dust. In addition to the technological
Fig. 3. Average percentage of individual PAHs in total PAHs bounded with TSP sampled in the coke oven battery sampling zones.
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Table 3 Comparison of diagnostic PAH ratios taken from literature and obtained in the study. Diagnostic ratio
This study
Coal combustion
BaA/(BaA + Ch)
0.47 (0.40–0.51)
0.46 [41] 0.50 [44] 0.2–0.35 [45]
Fl/(Fl + Py)
0.54 (0.50–0.60)
>0.5 [46–49] 00.57 [41,50]
BaP/(BaP + Ch)
0.39 (0.26–0.49)
0.180.49 [47] 0.46 [41] 0.5 [46,50,52]
0.47 [42]
0.86 [7] 0.40 [51]
BbF/BkF
1.03 (0.90–1.41)
3.5–3.9 [7] 3.53–3.87 [53]
2.06 [42]
0.8–1.1 [7] 0.76–1.45 [53]
BaP/BghiP
3.9 (1.37–12.18)
0.9–6.6 [54]
a
0.53 [49,50]
>1.25[50,55]
Coke oven
Wood combustion
Steel manufacture
0.45 [42]
0.48 [43]
0.62 [42]
0.4 [43]
5.1 [7] 1.32 [42]
BaA/Ch
0.89 (0.65–1.03)
0.70 [7]
BaP/R4 PAHa
0.26 (0.20–0.31)
0.9 [42]
R4 PAHa)/R13 PAH
0.41 (0.24–0.53) 1.19 (0.75–2.26)
4 rings/(5 + 6) ringsb b
Coal/coke
0.71 [43]
BaP + BbF + BkF + IP. (Fl + Py + BaA + Ch)/(BbF + BkF + BaP + DBA + BghiP + IP).
process that runs in the reactors, periodical operations of loading and unloading of chambers, accompanied by increased emissions of dust and gas, are carried out. The emission takes place into the open air with constantly changing: wind speed and direction and other meteorological parameters with the strong influence of heat emission. Coke production is also accompanied by the organized emission from the chimney due to battery firing and also from coke quenching tower. Taking into account strong convection above coke oven, and the following high elevation of thermal plume, depicted phenomena had no real effect on the results as well as emissions of PAHs from external sources. According to data from air quality monitoring in the area of Silesia Province concentration of PAHs in September does not exceed 30 ng/m3 [32,34,40], while the lowest concentration of PAHs measured in a course of our study was 660 ng/m3. The results as a set of the absolute values of concentrations were evaluated in order to find a general trend. Individual PAHs share present in the TSP (Fig. 3) were calculated along with diagnostic ratios. Comparison of percentages of individual PAHs in total indicates the dominance of Ch (16.5%), BaA (14.8%), BbF (12.3%) and BkA (11.9%). High and balanced in all sampling zones share of BaP (approximately 10.6%) should be pointed out. On the other hand shares of Ph, IP, BghiP vary in measuring zones. In the battery wall – coke side and pusher machine zones, a greatest share of four-and five-ring PAHs is noted. Only in battery wall – pusher side zone no significant differences in the proportions of all measured PAHs are visible. During the investigation one stated that considering number of rings in the particle, the 4-ring PAHs have the greatest share in total i.e. 0.43–0.66, next the 5-ring ones from 0.24 to 0.42. Mass shares of PAHs groups were estimated for investigated sampling zones. Share of 3 rings PAHs in TSP is not high and belongs to a range from below limit of detection to 0.08. Only share of PS2 is a lot higher – it gains value 0.31, six rings PAHs had been not detected in this sampling point. PAHs profiles reveal high similarity in all investigated zones and in every measurement. The most important common features are the highest share of 4 rings PAHs, the lower of 5 rings ones and the lowest of 6 rings particles. The main difference is the absence of 3 rings PAHs in some cases. Profiles of PAHs present in the TSP can be stated as diagnostic for emission from coke oven battery during coal carbonization process regardless of the place of emission and stage of the process.
Knowledge of diagnostic ratio enables the approximate identification of PAH sources [7,8,43,47,55]. In the paper diagnostic ratios BaA/(BaA + Ch), Fl/(Fl + Py), BaP/(BaP + Ch), BbF/BkF, BaP/BghiP, BaA/Ch have been calculated (Table 3). These coefficients are the same or similar to those, obtained by other authors [7,42] for coal combustions, coal/coke or coke ovens. However, the ratios of BaA/(BaA + Ch), BaP/BghiP and BaA/Ch can be stated as characteristic for coal carbonization process. Moreover, those values are similar to results obtained in other studies [7,8], in which BaA/(BaA + Ch) is equal 0.45 [42], BaP/BghiP ratio was higher than 5 [7], while BaA/Ch was equal to 0.9 [42] and 0.7 [7]. The data collected in Table 3 enables the determination of diagnostic ratios for evaluation of emission sources of PAHs connected with TSP i.e. BaP/R4 PAH, R4 PAH/R13 PAH and 4rings/(5 + 6) rings PAH. 4. Conclusion The samples of TSP present in the air were collected in different zones surrounding coke oven battery, thus the chemical transformations of investigated PAHs were limited to minimum. It can be assumed that obtained results give a good characteristic of the emission of PAHs during coke production. The instantaneous concentrations of PAHs varied in time in a quite wide range. However, despite this variability the profile of PAHs group remains constant in the number of aromatic rings in the particle. The diagnostic ratio calculation of chosen PAHs and its comparison with data available in the literature allowed to determine following ratios: BaA/(BaA + Ch), BaP/BghiP, BaA/Ch, BaP/R4 PAH, R4 PAH/R13 PAH and 4 rings/(5 + 6) rings PAHs. In case of first three ratios the literature data was confirmed, while other ratios were specific for the presented study. High concentrations of BaP and BaPeq in investigated air samples revealed the possible hazard for plant workers. Despite the short and periodical exposition for concentrations reaching 1290 ng/m3 of BaP and 2630 ng/m3 of BaPeq the inhaled doses are significant. Acknowledgement We would like to thank Mr Bogusław Komosin´ski for his help in the coke plant dust samples collection.
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Contents lists available at ScienceDirect
Fuel journal homepage: www.elsevier.com/locate/fuel
Polycyclic aromatic hydrocarbons in particulate matter emitted from coke oven battery Barbara Kozielska a,⇑, Jan Konieczyn´ski b a b
Silesian University of Technology, Faculty of Power and Environmental Engineering, Department of Air Protection, 2 Akademicka St., 44-101 Gliwice, Poland Institute of Environmental Engineering, Polish Academy of Sciences, 34 M. Skłodowskiej-Curie St., 41-819 Zabrze, Poland
h i g h l i g h t s
g r a p h i c a l a b s t r a c t
Determination of 13 PAHs in dust
Average percentage of individual PAHs in total PAHs bounded with TSP of the coke oven battery sampling zones.
captured in a close neighborhood of coke oven battery has been done. Characteristic for coking process ratios of selected pairs as well as PAH’s profiles in TSP were determined. Investigation was carried out on a plant fulfilling all BAT requirements. PAHs analyzes were done with use of gas chromatography techniques.
a r t i c l e
i n f o
Article history: Received 21 October 2011 Received in revised form 16 December 2014 Accepted 17 December 2014 Available online 29 December 2014 Keywords: Air pollutants TSP PAH Diagnostic ratios Poland
a b s t r a c t Coke oven battery is one of the main sources of fugitive total suspend particles (TSP) and polycyclic aromatic hydrocarbons (PAHs) in coke plants. In this study the content of selected PAHs associated with the TSP in the immediate vicinity of the coke oven battery Radlin (Poland) was investigated. TSP collection places were located on battery wall, battery roof, pusher machine and coal transfer car. Revealed TSP concentrations were within the range of 0.50–5.15 mg/m3, the total content of PAHs within wide range of 216.6–28018.9 lg/g. Regardless of the concentration level of PAHs connected with the TSP in the coke oven battery surrounding, it was found that four rings PAHs are the main fraction (50–70%). The high average concentrations of benzo[a]pyrene (BaP) and Toxicity Equivalent BaP (BaPeq) reaching 1.29 and 2.63 lg/m3 respectively in the immediate vicinity of coke oven battery, could pose a serious threat to the health of a coking plant workers. Calculated diagnostic ratios BaA/(BaA + Ch), Fl/(Fl + Py), BaP/ (BaP + Ch), BbF/BkF, BaP/BghiP, BaA/Ch are characteristic for the coking process. Ó 2014 Elsevier Ltd. All rights reserved.
1. Introduction
⇑ Corresponding author. Fax: +48 32 237 12 90. E-mail address: [email protected] (B. Kozielska). http://dx.doi.org/10.1016/j.fuel.2014.12.069 0016-2361/Ó 2014 Elsevier Ltd. All rights reserved.
Coke production is found to be the crucial environmental nuisance. This is caused by the fact, that it is not possible to make such process fully hermetic.
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The greatest total dust and gases emission source in the coking industry is the coke oven battery. Among emitted pollutants polycyclic aromatic hydrocarbons (PAHs) are present. The recent interest in emission of PAHs from national coke industry is caused by its high production potential (10 mln Mg/a) which results in its significant share in PAHs emission established at the level of 20 Mg/a, including benzo[a]pyrene – 8 Mg/a. It must be emphasized that, polish coke plants meet all the requirements of European emission standards. The determination of the coke plant impact on the environment mostly is done using emission factors. The estimated emission factors for total PAHs as well as for individual ones are different depending on place and measurement procedures e.g. in studies carried out in 1978–1989 by Bjorseth, Eisenhut, Tonelaar and Duiser the total PAHs emission factors were in range of 2.5– 15 g/Mg [1–4]. Despite significant differences in values some similarities also can be found. One is the concentration of particular PAHs group, which is the greatest for lighter, 3–4 rings PAHs (from 74 to 84 wt.%), and then for 5–6 rings PAHs (from 16 to 26 wt.%). It is also found that among 3-ring PAHs share of phenanthrene is very high and reaches up to 45.9% [5]. Further studies carried out by Bendrowski in 1995 allowed to established obligatory emission factors of benzo[a]pyrene, benzo[b]fluoranthene, benzo[k]fluoranthene and indeno[1,2,3–cd]pyrene as both, single compounds and their sum – R4 PAHs [6]. The determination of qualitative and quantitative composition of PAHs emitted from a given technological process and their appearance in gaseous and solid phases enables to specify PAHs emission source. In case of coke industry, profiles of PAH groups differ in number of rings in the particle or characteristic PAHs ratios (values of mass ratios of individual PAHs and PAH groups present in the dust) and thus are convenient to establish coke oven battery fingerprints and tracers. According to Khalili 89.8% share of naphthalene and 9.4% share of 3-ring PAHs in total amount of 20 determined PAHs can be stated as fingerprint of coke plant [7]. Fluorene present in the air is one of the coke plant tracers [8]. Harrison et al. found that common appearance of particular PAHs was the emission source marker. Hence, chrysene and benzo[k]fluoranthene are coal combustion markers, coronene and phenanthrene are combustion engines emission markers, pyrene, fluoranthene and phenanthrene are waste incineration plant markers, while heating oil combustion results in emission of fluorene, fluoranthene and pyrene together with benzo[b]fluoranthene and indeno[1,2,3-cd]pyrene [9]. In order to determine the share of emission source in PAHs concentration in air, the comparison of PAHs profiles mainly presented in TSP is made [10,11]. Comparing the results obtained in Belgium [12] it was found that ambient air close to steelworks contained anthracene, pyrene, benzo[g,h,i]perylene and chrysene what could be caused by emission from coke oven batteries. Analyses and measurements of PAHs concentration in both, gaseous and solid phases of air samples collected 100 m away from coke oven battery revealed that profiles of PAHs in ambient air significantly depended on wind direction and presence of other sources [13]. PAHs ratios in atmospheric particles have different values depending on emission source. The analysis of coke plant dust performed by Khalili and Simcik revealed characteristic, higher than 5 ratio of BaP/BghiP, 0.79 ratio of Ph/An, 0.7 ratio of BaA/Ch and 2.5 ratio of BeP/BaP [7,8]. In this case values of BaP/ BgP or Py/BaP ratios, indicated cars with combustion engines as the main emission source [14–16]. PAHs appear in either gaseous or solid phases or in both of them. Distribution of PAHs between gas and solid phase depends on environmental conditions i.e. ambient temperature, air humidity, particles concentration and PAHs properties i.e. molecular weight, vapor pressure, particles size, surface area and the nature of particulate [17–20], photochemical degradation and radical reactions [21,22]. Airborne PAHs with less than three aromatic
rings (mol wt. 128–178) are gaseous, whereas PAHs with five or more rings (mol wt. >228) occur in the solid phase [23–25]. Lee et al. established the level of PAHs bound to airborne particulates in ambient air around the traffic source in the range 28.3–67.3% (46.1% in average). Simultaneously, the mean particle phase distribution of total PAHs in the urban and rural atmospheres was only 18.7% and 20.6%, respectively [17]. Ravindra et al. indicated that concentration of PAHs in gaseous phase was 10 times higher than in particles of dust present in analyzed samples. However, the share of PAHs stated as hazardous reaches ca. 55% in solid phase, while in gaseous phase it is only 2% [12]. 2. Experimental The study was based on a modern coke oven battery in Radlin Coke Plant fulfilling best available technique (BAT) requirements, and it comprises determination of PAHs concentration in TSP in direct proximity to coke oven battery, investigation of PAHs profiles and characterization of their composition to indicate emission source markers. The battery was built in 2009, it contains 2 blocks which comprise 43 coking chambers of dimensions (mm) 15900 5000 500 each, its coke production capacity reaches 750 thousand Mg/a. The charging of chambers is done using stamp method, while coke quenching by means of wet method. The pneumatic sealing of ascension pipes closure is applied. For limitation of pollutants emissions during chambers discharging coke transfer machine is equipped with integrated suction hood followed by dedusting installation. The dedusting process is carried out in 2 devices arranged in series i.e. cyclone and bag filter [26]. Points, where air polluted with gases and dust emitted from the battery in unorganized manner were sampled, had been determined considering different phases and conditions of coking process. TSP samples were collected in the nearest surrounding of coke oven battery (Fig. 1). This manner of samples collection reduces the possible PAHs transformations, caused by chemical reactions i.e. oxidation, phototransformation and interaction with other compounds as well as influence of others PAHs sources to minimum. TSP samples were collected on 17th and 18th of September 2009 by StaplexÒ TFIA Series High Volume Air Samplers (The StaplexÒ Company, New York, USA). Sampler was equipped with SH 810 Filter Holder Assemblies. During the measurements, the weather conditions were as follows: temperature 15–16 °C, absence of rain, wind velocity below 3 m/s and pressure 973 hPa. The mass of the sampled dust was determined gravimetrically (Sartorius balance, resolution 0.01 g). Before each weighing, the filters were conditioned for at least 48 h at the air temperature of 20 ± 1 °C and air relative humidity of 50 ± 5% in the weighing room. The sampling was carried out for 1 h, the volumetric air flow was greater than 50 dm3/min and the volume of collected air reached about 3.5 m3. 2.1. Sample preparation and analysis of PAHs Samples of TSP was extracted from filters in ultrasonic bath with dichloromethane (CH2Cl2). The extract was percolated, washed and dried in helium atmosphere. The dry residue was diluted in propanol-2 (CH3CH(OH)CH3) and next distilled water was added to receive alcohol/water volume ratio 15/85. For selective purification, the obtained samples were solidified (SPE) via extraction in columns filled with octadecylsilane – C-18, (Supelclear™ ENVI-18 Tubes, Supelco USA). PAHs were eluted with the use of dichloromethane. The extract of PAHs was thickened by helium atmosphere to volume of 0.5 cm3. A Perkin Elmer Clarus 500 gas chromatograph equipped with a flame ionization detector (FID) was used. An RTX-5 (Restek)
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CS - battery wall – coke side; PS - battery wall – pusher side; RCS - battery roof – coke side; RPS - battery roof – pusher side; CTC - coal transfer car; PuM - pusher machine Fig. 1. Sampling places of TSP at coke oven battery in Radlin Coke Plant.
capillary column 30 m 0.32 mm 0.25 lm, with non-polar stationary phase was applied to separate sample components. The flow of carrier gas i.e. helium was equal to 1.5 cm3/min. The samples were introduced into split/splitless injector. Temperatures of the injector and detector were 240 °C and 280 °C respectively. The initial temperature of the GC oven was 60 °C which was held for 4 min, next it was increased by 10 °C/min until it reached 280 °C, then it was held constant for 14 min. The total time of the analysis was 40 min. The detector was provided with hydrogen (45 cm3/min) and air (450 cm3/min). 13 of 16 USEPA priority PAHs were analyzed – list of PAHs and suitable abbreviations are shown in Table 1. The quantitative analysis was done basing on the calibration curves prepared for 16 standard PAHs (Na, Acy, Ace, F, Ph, An, Fl, Py, BaA, Ch, BbF, BkF, BaP, DBA, BghiP, IP). The linear correlation between the peak surface areas and the PAH concentrations was checked within the range 10–40 ng/ll (correlation coefficients 0.99, PAH Mix PM-611 Ultra Scientific standard of the concentration 100 lg/ml of each PAH was used). The analysis of each sample-series was accompanied with the analysis of a blank sample. The correctness of the applied method was checked by the analysis of the NIST SRM 1649b reference material and comparison of the results with the certified concentrations of the investigated PAHs (analyses of three certified samples of dust, 0.2 g each). The standard recovery was from 92% to 111%.
3. Results and discussion During the sampling of TSP present in the air, its concentration referred to one hour measurement was determined. Obtained
values are in the vast range of 0.50–5.15 mg/m3. The highest concentration was obtained for coke transfer car, next one for the battery roof – coke side and pusher machine. The lowest value was measured at coke side. The overall concentration of dust was stated as moderate. Mean concentrations of TSP in sampling zones were shown in Fig. 2. Similar results were obtained by Mu et al. [27]. In four typical coke plants in China at the top of coke oven, they found TSP levels in the range of 1.48–3.45 mg/m3. It was found [28] that in a total mass of PM10 there is 2.98% R9 PAHs in coking plant ‘‘Jadwiga’’ in Zabrze, 0.64% R9 PAHs in coking plant ‘‘De˛bien´sko’’ in Czerwionka-Leszczyny and 2.77% coking
Table 1 List of PAHs and abbreviations used in the text. Compound
Chemical formula
Abbreviation
Molar mass (g/mol)
Naphthalene Acenaphtene Acenaphthylene Fluorene Phenanthrene Anthracene Fluoranthene Pyrene Benzo[a]anthracene Chrysene Benzo[b]fluoranthene Benzo[k]fluoranthene Benzo[a]pyrene Dibenzo[a,h]antracene Benzo[g,h,i]perylene Indeno[1,2,3-cd]pyrene
C10H8 C12H10 C12H8 C13H10 C14H10 C14H10 C16H10 C16H10 C18H22 C18H22 C20H12 C20H12 C20H12 C22H14 C22H12 C22H12
Na Acy Ace F Ph An Fl Py BaA Ch BbF BkF BaP DBA BghiP IP
128.17 154.21 152.20 166.22 178.23 178.23 202.25 202.25 228.29 228.29 252.31 252.31 252.31 278.35 276.33 276.33
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I – standard deviation Fig. 2. The average concentration of TSP in the coke oven battery sampling zones and content of 13 PAHs in TSP.
´ ski / Fuel 144 (2015) 327–334 B. Kozielska, J. Konieczyn Table 2 The average summary content of 13 PAHs and 4 PAHs in TSP, Toxicity Equivalent BaP (BaPeq) in ambient air in the coke oven battery sampling zones.
Battery wall – pusher side (PS) Battery wall – coke side (CS) Battery roof – pusher side (RPS) Battery roof – coke side (RCS) Pusher machine (PuM) Coal transfer car (CTC) a
R13 PAH
R4PAHa
(lg/g)
(lg/g)
BaPeq (ng/m3)
2697.0 15654.0 11512.3 15914.3 1323.4 14787.2
928.7 6549.1 4649.9 6298.1 558.5 5815.5
793.7 2117.9 2661.5 5960.3 444.3 1617.9
BaP + BbF + BkF + IP.
plant ‘‘Radlin’’ in Radlin. For presented work the mean percentage of the R13 PAHs in TSP is 1.07%. In the presented work the R13 PAHs percentage in TSP in sampling points remains in the range of 216.7–28018.9 lg/g. The values of the R4 PAHs (BaP, BbF, BkF, IP) used in the coke industry in general assessing the impact of coking on the environment [6], ranges from 108.1 to 11522.8 lg/g. They represent 24.50–53.07% of total PAHs (40.61% in average) – Table 2. Ambient concentration of R13 PAHs (g/m3) ranges from 0.66 to 1.36 for battery wall – pusher side, 9.11–14.09 for battery wall – coke side, 1.21–30.22 for battery roof – pusher side, 13.69–41.32 for battery roof – coke side, 1.48–2.99 for pusher machine and 1.12–14.06 for coal transfer car. Liberti et al., carried out environmental monitoring at cokeoven batteries at the Taranto (Italy). They found R17 PAHs concentration (gaseous and particulate phases) for top-pusher machine side, top-coke side, pusher machine and pusher machine side 628 lg/m3, 426 lg/m3, 274 lg/m3, 329 lg/m3, respectively [29]. In turn Mu et al. in ambient air on the top of coke ovens stated concentration of R16 PAHs were contained in a range of 1.58– 146.98 lg/m3 [27]. In a gaseous phase the greatest share belongs to two rings (>93.3%) and three rings (87.4%) PAHs (Na, Acy, Ace, F, Ph, An) while in TSP five (92.3%) and six rings (99.1%) PAHs (BbF, BkF, BaP DBA, BghiP, IP). Four rings PAHs might appear in both gaseous phase and particle bound [30]. Among investigated compounds BaP is of a great interest considering its well known carcinogenic and mutagenic properties. The concentration of BaP in TSP sampled in coke oven battery zones was in the range of 6.7–3355.9 lg/g. The lowest value was obtained for battery wall – pusher side (PS2), while the greatest one for coal transfer car (CTC1). The concentration of BaP in ambient air was in the wide range of 109.99 ng/m3 for coal transfer car
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(CTC2), up to 4467.80 ng/m3 for battery roof – coke side (RCS1). The exception was the one measuring point on battery wall – pusher side (PS2), where the concentration 8.12 ng/m3 of BaP was relatively low. Ambient concentrations of TSP-related BaP in the neighborhood of the coke oven battery are alarmingly high and close to the extremely high concentrations of BaP found in the road tunnel in Nanjing (China) (2377 ng/m3 and 2534 ng/m3 in summer and winter, respectively) [31]. For comparison, concentrations of TSP-related BaP next to roadway in Katowice and Sosnowiec (Poland) were 10.82 ng/m3, and 9.91 ng/m3 respectively [32], while in Agra (India) in industrial-cum-residential it was 140 ng/ m3 [33]. Toxicity Equivalent BaP (BaPeq) was in the range of 169.96 ng/ m3 (coal transfer car – CTC2) to 11390.96 ng/m3 (battery roof – coke side – RCS1) with exception of battery wall – pusher side (PS2), where BaPeq was 32.69 ng/m3. In Table 2 average values of BaPeq in particular sampling zones are presented. Revealed BaPeq values are very high. Similar results were obtained by Mu et al. on the top of coke oven – 3140 ng/m3 [27]. Very high concentrations of BaP and BaPeq create health hazard for plant workers. For comparison, the BaPeq in the cities of Upper Silesia were: in winter 2007 in Zabrze for PM2.5–41.72 ng/m3, PM10–41.91 ng/m3 [34], in the heating season 2007/2008 PM2.5–31.70 ng/m3, PM10– 31.81 ng/m3 [35]. In Katowice (2009–2010) BaPeq concentration in PM2.5 for urban traffic was 2.88–474.24 ng/m3, while for the urban background 0.95–195.86 ng/m3 [36]. These values are much higher than for example in Xiamen: 0.85 ng/m3 and 0.92 ng/m3 for PM10 and PM2.5 bound PAH [37] or Shanghai – 15.77 ng/m3 [38]. Focusing on PAHs contained in the TSP is fully reasonable. Although PAHs in ambient air occurs mainly in a gaseous phase, the parts of them creating the highest hazard to human’s health appear mostly as bounded with TSP. For instance, Hassan and Khoder found that samples collected in summer and winter in an urban area in Dokki (Giza, Egypt) contain only 22.58% and 36.97% PAHs in TSP respectively. However, PAHs in the particulate phase pose higher potential health risk because the mean relative contributions of the total carcinogenic activity (concentrations) of all PAHs to the total concentrations of PAHs were 29.37% and 25.15% in the particulate phase and 0.76% and 0.92% in the gaseous phase during the summer and winter [39]. Very wide range of concentrations of PAHs in the studied samples of dust collected from the ambient air around battery results from its design and operation. It is worth mentioning that this is the installation consisting of dozens of reactors with reduced leakage, which run analogous processes, but in a different phase. Each phase of the process is characterized by intensity and composition of manufactured gas and dust. In addition to the technological
Fig. 3. Average percentage of individual PAHs in total PAHs bounded with TSP sampled in the coke oven battery sampling zones.
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Table 3 Comparison of diagnostic PAH ratios taken from literature and obtained in the study. Diagnostic ratio
This study
Coal combustion
BaA/(BaA + Ch)
0.47 (0.40–0.51)
0.46 [41] 0.50 [44] 0.2–0.35 [45]
Fl/(Fl + Py)
0.54 (0.50–0.60)
>0.5 [46–49] 00.57 [41,50]
BaP/(BaP + Ch)
0.39 (0.26–0.49)
0.180.49 [47] 0.46 [41] 0.5 [46,50,52]
0.47 [42]
0.86 [7] 0.40 [51]
BbF/BkF
1.03 (0.90–1.41)
3.5–3.9 [7] 3.53–3.87 [53]
2.06 [42]
0.8–1.1 [7] 0.76–1.45 [53]
BaP/BghiP
3.9 (1.37–12.18)
0.9–6.6 [54]
a
0.53 [49,50]
>1.25[50,55]
Coke oven
Wood combustion
Steel manufacture
0.45 [42]
0.48 [43]
0.62 [42]
0.4 [43]
5.1 [7] 1.32 [42]
BaA/Ch
0.89 (0.65–1.03)
0.70 [7]
BaP/R4 PAHa
0.26 (0.20–0.31)
0.9 [42]
R4 PAHa)/R13 PAH
0.41 (0.24–0.53) 1.19 (0.75–2.26)
4 rings/(5 + 6) ringsb b
Coal/coke
0.71 [43]
BaP + BbF + BkF + IP. (Fl + Py + BaA + Ch)/(BbF + BkF + BaP + DBA + BghiP + IP).
process that runs in the reactors, periodical operations of loading and unloading of chambers, accompanied by increased emissions of dust and gas, are carried out. The emission takes place into the open air with constantly changing: wind speed and direction and other meteorological parameters with the strong influence of heat emission. Coke production is also accompanied by the organized emission from the chimney due to battery firing and also from coke quenching tower. Taking into account strong convection above coke oven, and the following high elevation of thermal plume, depicted phenomena had no real effect on the results as well as emissions of PAHs from external sources. According to data from air quality monitoring in the area of Silesia Province concentration of PAHs in September does not exceed 30 ng/m3 [32,34,40], while the lowest concentration of PAHs measured in a course of our study was 660 ng/m3. The results as a set of the absolute values of concentrations were evaluated in order to find a general trend. Individual PAHs share present in the TSP (Fig. 3) were calculated along with diagnostic ratios. Comparison of percentages of individual PAHs in total indicates the dominance of Ch (16.5%), BaA (14.8%), BbF (12.3%) and BkA (11.9%). High and balanced in all sampling zones share of BaP (approximately 10.6%) should be pointed out. On the other hand shares of Ph, IP, BghiP vary in measuring zones. In the battery wall – coke side and pusher machine zones, a greatest share of four-and five-ring PAHs is noted. Only in battery wall – pusher side zone no significant differences in the proportions of all measured PAHs are visible. During the investigation one stated that considering number of rings in the particle, the 4-ring PAHs have the greatest share in total i.e. 0.43–0.66, next the 5-ring ones from 0.24 to 0.42. Mass shares of PAHs groups were estimated for investigated sampling zones. Share of 3 rings PAHs in TSP is not high and belongs to a range from below limit of detection to 0.08. Only share of PS2 is a lot higher – it gains value 0.31, six rings PAHs had been not detected in this sampling point. PAHs profiles reveal high similarity in all investigated zones and in every measurement. The most important common features are the highest share of 4 rings PAHs, the lower of 5 rings ones and the lowest of 6 rings particles. The main difference is the absence of 3 rings PAHs in some cases. Profiles of PAHs present in the TSP can be stated as diagnostic for emission from coke oven battery during coal carbonization process regardless of the place of emission and stage of the process.
Knowledge of diagnostic ratio enables the approximate identification of PAH sources [7,8,43,47,55]. In the paper diagnostic ratios BaA/(BaA + Ch), Fl/(Fl + Py), BaP/(BaP + Ch), BbF/BkF, BaP/BghiP, BaA/Ch have been calculated (Table 3). These coefficients are the same or similar to those, obtained by other authors [7,42] for coal combustions, coal/coke or coke ovens. However, the ratios of BaA/(BaA + Ch), BaP/BghiP and BaA/Ch can be stated as characteristic for coal carbonization process. Moreover, those values are similar to results obtained in other studies [7,8], in which BaA/(BaA + Ch) is equal 0.45 [42], BaP/BghiP ratio was higher than 5 [7], while BaA/Ch was equal to 0.9 [42] and 0.7 [7]. The data collected in Table 3 enables the determination of diagnostic ratios for evaluation of emission sources of PAHs connected with TSP i.e. BaP/R4 PAH, R4 PAH/R13 PAH and 4rings/(5 + 6) rings PAH. 4. Conclusion The samples of TSP present in the air were collected in different zones surrounding coke oven battery, thus the chemical transformations of investigated PAHs were limited to minimum. It can be assumed that obtained results give a good characteristic of the emission of PAHs during coke production. The instantaneous concentrations of PAHs varied in time in a quite wide range. However, despite this variability the profile of PAHs group remains constant in the number of aromatic rings in the particle. The diagnostic ratio calculation of chosen PAHs and its comparison with data available in the literature allowed to determine following ratios: BaA/(BaA + Ch), BaP/BghiP, BaA/Ch, BaP/R4 PAH, R4 PAH/R13 PAH and 4 rings/(5 + 6) rings PAHs. In case of first three ratios the literature data was confirmed, while other ratios were specific for the presented study. High concentrations of BaP and BaPeq in investigated air samples revealed the possible hazard for plant workers. Despite the short and periodical exposition for concentrations reaching 1290 ng/m3 of BaP and 2630 ng/m3 of BaPeq the inhaled doses are significant. Acknowledgement We would like to thank Mr Bogusław Komosin´ski for his help in the coke plant dust samples collection.
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