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Hazardous Compounds in Urban Pm in the Central Part of Upper Silesia (Poland) in Winter

Hazardous Compounds in Urban Pm in the Central Part of Upper Silesia (Poland) in Winter Thirteen fractions of ambient dust were investigated in Zabrze, a typical urban area in the central part of Upper Silesia (Poland), during a heating season. Fifteen PAH and Cr, Mn, Co, Ni, As, Se, Cd, Pb contents of each fraction were determined. The dust was sampled with use of a cascade impactor and chemically analyzed with an energy dispersive X-ray fluorescence spectrometer (PANalytical Epsilon 5) and a gas chromatograph with a flame ionisation detector (Perkin Elmer Clarus 500). The concentrations of PM1 and the PM1-related PAH and elements were much higher than the ones of the coarse dust (PM2.5-10) and the substances contained in it. The concentrations of total PAH and carcinogenic PAH were very high (the concentrations of PM1-, PM2.5-, and PM10-related BaP were 16.08, 19.19, 19.32 ng m-3, respectively). The municipal emission, resulted mainly from hard coal combustion processes, appeared to be the main factor affecting the air quality in Zabrze in winter. INTRODUCTION Despite clear positive statistical relations between the concentrations of ambient particulate matter (PM) and the health effects [44] the biological mechanisms of the toxic activity of PM are not entirely known [5, 11]. Still it is not definitely settled which factor, the concentration and the granularity or the chemical composition, determines the hazard from PM [1, 53]. Anyway, polycyclic aromatic hydrocarbons (PAH) and PM-related metals are considered to be the most hazardous components of PM (the most often investigated PAH are: acenaphtene (Acy), acenaphthylene (Ace), anthracene (An), benzo(a) anthracene(BaA), benzo(a)pyrene (BaP), benzo(e)pyrene (BeP), benzo(b)fluoranthene (BbF), benzo(j)fluoranthene (BjF), benzo(k)fluoranthene (BkF), benzo(g,h,i)perylene (BghiP), chrysene (Ch), dibenzo(a,h)anthracene (DBA), fluoranthene (Fl), fluorene (F), phenanthrene (Ph), pyrene (Py) and indeno(1,2,3-cd)pyrene (IP), and metals: As, Be, Cd, Co, Cr, Hg, Mn, Ni, Pb, and Se [34, 56]. The goal of the work was to determine the mass distribution of eight elements (Cr, Mn, Co, Ni, As, Se, Cd, Pb) and fifteen PAHs (Acy, Ace, F, Ph, An, Fl, Py, BaA, Ch, BbF, BkF, BaP, DBA, BghiP, IP) between three PM fractions (PM1, PM1-2.5, PM2.5-10) and their ambient concentrations in Zabrze, southern Poland. From the air protection point of view, Zabrze is located in the most interesting region of Poland ­ Upper Silesia ­ where the recent three decades of economic changes forced the greatest in Poland drop of industrial air pollution and where old steel works, cokeries and coal mines, together with road traffic, are responsible for high concentrations of ambient dust [40, 41, 49]. Investigations were done in a winter heating season, when the emission from combustion of fossil fuels for energy production (especially municipal) causes very high PM concentrations [41, 15]. METHOD The site, selected in Zabrze for the experiment, is representative of the typical air-pollution conditions in the central part of Upper Silesia - by the Directive 2008/50/EC definition [7], it is an urban background measuring point (Fig. 1). The effects of the industrial and municipal emissions on living quarters of the agglomeration are represented and may be observed very well there. Fig. 1. Location of sampling site Ambient dust was sampled with the use of a thirteen stage DEKATI low pressure impactor (DLPI), which collects thirteen PM fractions (0.03-0.06, 0.06-0.108, 0.108-0.17, 0.17-0.26, 0.26-0.4, 0.4-0.65, 0.65-1.0, 1.0-1.6, 1.6-2.5, 2.5-4.4, 4.4-6.8, 6.8-10.0, >10 m) onto thirteen substrate filters. The principle of DLPI operating may be found in [19]. PM was sampled from 26 October 2007 to 22 March 2008 (a whole heating season). A single sample-taking lasted for about one week. The seven thirteen-substrate samples from the period 26 October ­ 27 December 2007 were analyzed for PAH, the remaining seven ones from the period 11 January - 22 March 2008 ­ for the elemental composition. The mass of the dust collected on aluminum (PAH analyzes) and polycarbonate (elemental composition) substrates was determined by weighing the substrates before and after exposure on a Mettler Toledo balance. Before weighing, the substrates were kept in the weighing room for 48 hours (temperature 20±2°C, relative air humidity 48±5%). The concentrations of the fractions of PM were computed from the volume of air passed through the impactor and the masses of the dust collected on its stages. The samples for the PAH analysis, till analyzing, were kept in a refrigerator in tight and lightproof containers. The elemental composition of each of the seven samples of each of the 13 PM fractions from the period 11 January - 22 March 2008 was determined by applying energy dispersive X-ray fluorescence (EDXRF). The ambient concentrations of Cr, Mn, Co, Ni, As, Se, Cd, Pb were determined and the average ambient concentrations (arithmetic means) of each element were computed for each fraction. A PANalytical Epsilon 5 was used. The measurements were done under vacuum, the analysis time for a single sample was 4800 s. The X-ray tube was adjusted depending on a secondary target used: 25 keV and 25 mA for Al, 40 keV and 15 mA for Ti, 40 keV and 15 mA for Fe, 75 keV and 8 mA for Ge, 100keV and 6mA for Zr, 100keV and 6mA for Al2O3. The element concentrations were determined by comparing the results with the calibration curves. Thin-layer single-element Micromatter standards were used to calibrate the apparatus [61]. Weekly measurements of the NIST SRM2873 standards (except for Co, whose recovery was 39%, recoveries of remaining elements were between 91 and 116% of the certified value) and monthly measurements of the monitor were routinely performed to control the quality of the analytical procedure. The detection limits were from 0.2 ng cm-2 for Se to 11.6 ng cm-2 for As. For each of the 13 PM fractions, all its seven samples from the period 26 October - 27 December 2007 were extracted together in dichloromethane (CH2Cl2) in an ultrasonic bath. The extract was percolated, washed and dried by evaporating in the helium atmosphere. The dry residue was diluted in propanol-2 (CH3CH(OH)CH3) and distilled water was added to receive the propanol-2 to water proportion 15/85 (v/v). For selective purification, the resulting samples were solidified (SPE) by extracting in columns filled with octadecyl (C18, Supelco). PAH were eluted with use of dichloromethane (CH2Cl2). The extract of the PAH fraction was condensed in the helium atmosphere to the volume of 0.5 cm3. The samples were analyzed on a Perkin Elmer Clarus 500 gas chromatograph with a flame ionization detector (FID). An RTX-5 Restek capillary 30 m × 0.32 mm × 0.25 m column was used to separate the sample components. The flow of the carrier gas, helium, was 1.5 cm3 min-1. The calibration curves for the 15 PAH standards were used in the quantitative determinations. The linear correlation of the peak surfaces with the PAH concentrations was checked in the concentration range 1­50 ng l-1. The correlation coefficients ranged from 0.95 to 0.99. The time of the whole analysis was 40 min. FID was provided with hydrogen (45 cm3 min-1) and air (450 cm3 min-1). The recoveries of PAH, ranging from 85% to 93%, were determined using a standard containing the 15 PAH. RESULTS AND DISCUSSION The average concentration of PM10 (PM10 = PM1 + PM1-2.5 + PM2.5-10) in the last quarter of 2007 exceeded 46 g m-3, in the first quarter of 2008 ­ 38 g m-3 (Table 1). In most European countries the yearly PM10 concentration has been limited for about twenty years (in Poland since 1998) and its highest permissible value is 40 g m-3. The Table 1. Concentrations of ambient dust (PM, g m-3), and of 15 PAH and 8 elements (ng m-3) related to three fractions of ambient dust in Zabrze, in the central part of Upper Silesia, Poland, in winter PM11) PM PM 4) 5) PM1-2.52) 7.79 7.66 1.11 17.26 <DL 0.04 0.49 <DL 0.27 9.54 0.10 0.05 0.17 0.95 0.28 3.49 4.50 3.57 3.78 2.09 2.41 3.11 0.09 0.36 0.86 PM2.5-103) 5.18 4.98 1.33 20.66 <DL 0.06 0.35 <DL 0.14 7.50 <DL <DL 0.38 0.51 0.25 0.08 0.12 0.05 0.16 0.24 0.27 0.13 <DL <DL <DL 25.55 33.65 2.54 59.99 <DL6) 0.17 2.14 <DL 0.75 23.56 0.19 0.33 1.36 4.07 0.88 15.80 18.03 17.78 17.11 12.84 13.76 16.09 0.73 3.01 6.12 Cr Mn Co Ni As Se Cd Pb Acy Ace F Ph An Fl Py BaA Ch BbF BkF BaP DBA BghiP IP 1) sum of concentrations of dust, element or compound in fractions 0.03-0.06, 0.06-0.108, 0.108­0.17, 0.17­0.26, 0.26­0.4, 0.4­0.65, 0.65­1.0 m 2) sum of concentrations of dust, element or compound in fractions 1.0­1.6, 1.6­2.5 m 3) sum of concentrations of dust, element or compound in fractions 2.5­4.4, 4.4­6.8, 6.8­10.0 m 4) average concentration from 11 January to 22 March 2008 5) average concentration from 26 October to 27 December 2007 6) concentrations below detection limit high PM10 concentrations during a half-year in Zabrze may mean violating this limit. The concentrations of PM2.5 (PM2.5 = PM1 + PM1-2.5) also were high; in the winter 2007/2008 they exceeded the limit 25 g m-3 [7]. PM2.5 and PM1, the fractions of respirable dust, contributed no less than 89 and 72% to PM10, respectively. The average concentrations of the eight toxic elements in Zabrze in the period 11 January ­ 22 March 2008 were low compared to their permissible values both domestic and EU ones, [6,13]. All, except the Cd concentration, were at least 10 times lower than their yearly limits. Because in summer the concentrations of PM and of the PM-related elements are usually lower, their yearly concentrations are not expected to exceed the yearly limits. The concentrations of Co and Se for each PM fraction were very low, lower than their detection limits: 0.1 ng m-3 for Se and 0.2 ng m-3 for Co. In the period 11 January - 22 March 2008, the concentrations of PM1 were high, the eight elements assumed the greatest concentrations as the PM1-related ones (Table 1). In Zabrze all these elements come probably from combustion and occur in PM1 in metal oxides, sulfates and chlorides. The enrichment coefficients [14, 51, 66], presented in Figure 2, confirm the fact. Only EF for PM1-2.5- and for PM2.5-10-related Ni are lower than 10. EF for the rest of the elements are very high, for PM1-related Cr and Mn higher than 100, for As and Pb higher than 1000. It reflects a strong anthropogenic effect on the winter concentrations of these PM-related elements in Zabrze. Seeming not very high compared to the air quality standards, the winter ambient concentrations of the toxic elements in Zabrze are higher than their winter concentrations in other regions of Europe (Table 2). The high concentrations of Pb, Cd, As, the lower than in other regions concentration of Ni (tracer of combustion of oil in typical European urban areas, [65]) and the results from the investigations of the smog episode in Zabrze in January 2006 [41] suggest the combustion of low-quality coal in domestic furnaces (municipal emission) as the source of these elements in Zabrze in winter. 100000 PM1 10000 1000 EFs 100 10 1 Ni Cr Mn As Pb Cd PM1-2.5 PM2.5-10 EFx for the element x is referred to the concentration CSi of Si, a marker element for the Earth crust-EFSi=1 (average Si concenttrations in Zabrze in January­March 2009 were: 122.8 ng m-3 for PM1, 94.9 ng m-3 for PM1-2.5, 172.6 ng m-3 for PM2.5-10). The chemical characterization of the Earth upper continental crust is taken from Wedepohl; 1995 [66] Fig. 2. EF for PM-related elements in Zabrze in winter 2008 Table 2. Ambient concentrations of elements related to various PM fractions at various sites in the world Location As 2.14 2.63 2.98 2 3 6.83 0.3 1.7 2.2 0.6 PM2.5 PM10 0.70 0.2 4.0 4.1 0.3 12.6 9.2 2 5 2.3 1.3 8.4 10.6 1.2 80.5 128.5 3.3 6.9 6.9 49.7 5.5 24.3 1.16 4.98 97.91 24.6 49.8 9 18 12 2.7 10.4 21.5 4 25.6 44.7 4.0 4.6 1.02 3.65 77.25 0.75 2.54 59.99 Cd Cr Mn Ni 0.17 0.21 0.27 17.7 17.3 7 9 3.4 1.59 3.4 3 15.3 15.3 97.8 41.7 PM1 Jan-Mar 2008 PM2.5 PM10 Jan 2006 PM10 PM1 PM2.5 PM2.5 PM2.5 PM2.5 PM2.5 PM10 PM1 PM2.5 PM10 Winter 2002 Winter 2003 Oct-Dec 2003 Jan-Mar 2005 Feb 2006 2005-2006 Nov 2007-Feb 2008 Spring 2009 PM2.5 Sampling period Fraction Concentration, ng·m-3 Pb 23.56 33.1 40.6 184.7 223.6 35 55 54 5.45 5.7 58.5 75.3 17 630.8 420.7 275.8 263.3 Zabrze (Poland); urban background a Zabrze (Poland); urban background [41] Milan (Italy); residential-commercial area [63] Menen (Belgium); suburban/industrial [38] Athens (Greece); suburban [62] Cartagena (Spain); suburban [35] Seoul (Korea); residential [39] Barcelona (Spain); urban background [42] Dehli (India), urban [55] Ulsan (Korea), residential area [25] this study The winter ambient concentrations of total PAH (PAH) in Zabrze were high - the concentrations of PM1- and PM2.5-related PAH were 128.1 ng m-3 and 153.9 ng m-3, respectively. PM1-related PAH were 82% and PM2.5-related PAH were 98% of PM10-related PAH. The concentrations of PM1-related PAH were about 5 times greater than the concentrations of PM1-2.5-related PAH.All PM fractions were rich in 4- and 5-ring PAH, which were no less than 89% of PAH. Among all PM-related PAH, Py, BaAand Ch had the greatest concentrations (PM1-related: 18.03 ng m-3, 17.78 ng m-3, 17.11 ng m-3, respectively). Fl, BbF, BkF, BaP ­ the compounds whose presence and high concentrations in atmospheric air indicate stationary combustion had also great ambient concentrations (12.84­16.09 ng m-3, PM1-related) and contributions to PAH. The proportion CPAH/PAH of the concentration of CPAH (total combustion PAH: Fl, Py, BaA, BbF, BkF, BaP, BeP, IP and BghiP) to the concentration of PAH, expresses the effect of stationary combustion on the PAH concentrations [47, 48, 54]. In Zabrze it was equal to 0.82 for PM1, 0.79 for PM1-2.5 and 0.41 for PM2.5-10- in winter PM1- and PM1-2.5-related PAH come from stationary combustion and PM2.5-10-related PAH ­ from combustion of fuels in car engines [47, 48]. The diagnostic ratios (selected proportions of the concentrations of PAH) for PM1and PM1-2.5-related PAH ([BaA]/([BaA]+[Chry]) equal to 0.51 for PM1 and 0.49 for PM1-2.5 or [BaA]/[BaP] equal to 1.11 for PM1 and 1.15 for PM1-2.5) show that PM1- and PM1-2.5-related PAH came mainly from coal combustion [59,67,68]. According to some authors [26], the winter [BaA]/[BaP] for PM1 and PM1-2.5 in Zabrze are indicative of wood burning. Also [BbF]/[BkF] equal to 0.93, 0.87 and 0.89 for, respectively, PM1, PM1-2.5 and PM2.5-10 suggest wood burning [30]. In turn, the proportions [BaA]/[BaP], [BaA]/([BaA]+[Chry]), [Ph]/([Ph]+[An]) for PM2.5-10-related PAH (0.38, 0.24, 0.67) suggest combustion of gasoline and oil in car engines as the PM2.5-10-related PAH origin [18,26,67] - in winter, at low air temperatures, the gaseous PAH from car engines tend to rapidly condense on big dust particles. The values of [BbF]/[BkF] equal to 0.74, 0.44 and 0.40 for, respectively, PM1, PM1-2.5 and PM2.5-10 suggest the vehicular origin of not only PM2.5-10-related but also of PM1- and PM1-2.5-related PAH in Zabrze in winter [16,47,48,67,68]. In Table 3, the winter concentrations of PM1-, PM2.5- and PM10-related PAH and BaP in Zabrze are compared with the winter concentrations of PAH and BaP at various sites in the world. The wide range of the concentrations of, equally, PAH and BaP is due to the differences in the number of PAH, meteorological conditions, local PAH sources etc. Nevertheless, the greatest concentrations of PM2.5-related BaP and PAH occur in Poland (Zabrze and Bytom, Upper Silesia). In other European cities, at the sites beyond the effect of vehicular and industrial emissions like in Zabrze, the concentrations of PM2.5-related BaP were from 0.33 ng m-3 in Amsterdam (the Netherlands) to 48.00 ng m-3 in Prague, (the Czech Republic) [52]. In Zabrze these concentrations were several times higher. The concentrations of PAH and BaP in Asiatic cities, such as Fashun (China) [21], Delhi (India) [55] and Tiruchirappalli (India) [32], were much greater than in Europe and closer to the winter concentrations in Zabrze. The hazard for humans from an individual ambient PAH is expressed relative to the hazard from BaP, whose toxicity is well characterized as the toxicity equivalency factor (TEF). TEF for BaP is equal to 1, TEF equal to 0 means lack of carcinogenicity of a compound. The hazard from a mixture of PAH is expressed as the BaP equivalent Table 3. Ambient concentrations of BaP and PAH related to various PM fractions at various sites in the world Location Zabrze (Poland), urban backgroundb Bytom (Poland), urban background (T1) [22] Bytom (Poland), city center (T2) [22] Duisburg (Germany), urban background [52] Prague (Czech Republic), urban background [52] Amsterdam (Netherlands), urban background [52] Bangkok (Thailand), urban [37] Atlanta (USA), urban [27] Zagreb (Croatia), urban [57] Fushun (China); urban background [21] Virolahti (Finland), regional background [29] Flanders (Belgium), urban background [64] Rome (Italy), downtown [4] Sampling period Fraction PM1 Concentration, ng·m-3 BaP 16.08 19.19 19.32 6.49 11.12 6.49 19.84 1.05 1.10 3.03 3.15 0.33 1.3 0.27 3.18 3.04 10.71 12.69 0.52 0.69 0.73 1.18 9.9 6.9 0.83 3.2±1.0 6.2±3.9 8.7-24.1 PAHa 128.10 (15) 153.10 (15) 156.11 (15) 85.52(16) 120.69(16) 80.36(16) 128.64(16) 12.63 (32) 15.76 (32) 48.00 (32) 55.11 (32) 7.25 (32) 12.59 (16) 2.86 (28) 21.23 (6) 21.78 (6) 261.82 (13) 334.26 (13) 7.54 (13) 14.53 (13) 13.9 (13) 82.24 (15) 6.70 (14) 7.77 (14) 7.98 (14) 96 (16) 81.5 (16) 11 (11) 32.7±11.8 (13) 75.1±32.7 (13) 136-371.5 (9) Oct ­ Dec 2007 PM2.5 PM10 PM2.5 PM10 PM2.5 PM10 PM2.5 PM10 PM2.5 PM10 PM2.5 PM10 PM2.5 PM2.5 PM10 PM2.5 PM10 PM1 PM2.5 PM10 PM10 PM1 PM2.5 PM10 PM2.5 PM10 PM2.5 PM2.5 PM2.5 Feb ­ Mar 2007 Feb ­ Mar 2007 Sep ­ Nov 2002 Nov 2002 ­ Jan 2003 Jan ­ Mar 2003 Nov 2002 ­ Apr 2003 Oct ­ Dec 2004 Winter 2004 Dec 2004 ­ Feb 2005 Winter 2006 Oct 2006 ­ Mar 2007 Oct 2007 ­ Feb 2008 Dehli (India), urban [55] Augsburg, (Germany) urban aerosol [43] Kaunas (Lithuania), urban [20] Tiruchirappalli (India), urban atmosphere [32] a b Nov 2007 ­ Feb 2008 Feb ­ Mar 2008 location 1 location 2 Winter 2009 Dec 2009 ­ Feb 2010 the number of PAH taken to compute PAH concentration is in parentheses this study (BEQ), which is the sum of the products of the concentrations of individual PAH in the mixture and their TEF [36]. In Zabrze, BEQ for PM2.5 and PM10 were very high in winter (31.70 ng m-3 and 31.81 ng m-3), much higher than in Shanghai (15.77 ng m-3; [10]) or some Japanese cities (BEQ around 2 ng m-3 [58]), where the ambient PAH concentrations were very high. In Zabrze, BEQ for PM1 was 26.73 ng m-3. CONCLUSIONS In Zabrze, in winter, the greatest parts of the PM-related PAH and elements accumulate in the finest PM fractions. The ambient fine particles occur in much greater amounts than coarse particles (PM2.5-10), and the ambient concentrations of the toxic substances they contain, especially carcinogenic PAH, are very high. After penetration into the respiratory system, the finest particles (PM1) reach the pulmonary alveoli where 60-80% of the elements brought with them pass into blood [45]. This is why the toxicity related to PAH [12] and transitive metals [60] is greater for fine than for coarse dust. The correlations between PAH content and cytotoxicity, mutagenity and DNA reactivity are higher for fine than coarse dust [3, 12, 31]. Such high winter concentrations and toxic component content of PM1 cause health hazard for the inhabitants of Zabrze, yet more serious because of its periodic occurrence and several months' duration. ACKNOWLEDGMENTS The work was partially supported by grant No. N N523 564038 from the Polish Ministry of Science and Higher Education. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Archives of Environmental Protection de Gruyter

Hazardous Compounds in Urban Pm in the Central Part of Upper Silesia (Poland) in Winter

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Abstract

Thirteen fractions of ambient dust were investigated in Zabrze, a typical urban area in the central part of Upper Silesia (Poland), during a heating season. Fifteen PAH and Cr, Mn, Co, Ni, As, Se, Cd, Pb contents of each fraction were determined. The dust was sampled with use of a cascade impactor and chemically analyzed with an energy dispersive X-ray fluorescence spectrometer (PANalytical Epsilon 5) and a gas chromatograph with a flame ionisation detector (Perkin Elmer Clarus 500). The concentrations of PM1 and the PM1-related PAH and elements were much higher than the ones of the coarse dust (PM2.5-10) and the substances contained in it. The concentrations of total PAH and carcinogenic PAH were very high (the concentrations of PM1-, PM2.5-, and PM10-related BaP were 16.08, 19.19, 19.32 ng m-3, respectively). The municipal emission, resulted mainly from hard coal combustion processes, appeared to be the main factor affecting the air quality in Zabrze in winter. INTRODUCTION Despite clear positive statistical relations between the concentrations of ambient particulate matter (PM) and the health effects [44] the biological mechanisms of the toxic activity of PM are not entirely known [5, 11]. Still it is not definitely settled which factor, the concentration and the granularity or the chemical composition, determines the hazard from PM [1, 53]. Anyway, polycyclic aromatic hydrocarbons (PAH) and PM-related metals are considered to be the most hazardous components of PM (the most often investigated PAH are: acenaphtene (Acy), acenaphthylene (Ace), anthracene (An), benzo(a) anthracene(BaA), benzo(a)pyrene (BaP), benzo(e)pyrene (BeP), benzo(b)fluoranthene (BbF), benzo(j)fluoranthene (BjF), benzo(k)fluoranthene (BkF), benzo(g,h,i)perylene (BghiP), chrysene (Ch), dibenzo(a,h)anthracene (DBA), fluoranthene (Fl), fluorene (F), phenanthrene (Ph), pyrene (Py) and indeno(1,2,3-cd)pyrene (IP), and metals: As, Be, Cd, Co, Cr, Hg, Mn, Ni, Pb, and Se [34, 56]. The goal of the work was to determine the mass distribution of eight elements (Cr, Mn, Co, Ni, As, Se, Cd, Pb) and fifteen PAHs (Acy, Ace, F, Ph, An, Fl, Py, BaA, Ch, BbF, BkF, BaP, DBA, BghiP, IP) between three PM fractions (PM1, PM1-2.5, PM2.5-10) and their ambient concentrations in Zabrze, southern Poland. From the air protection point of view, Zabrze is located in the most interesting region of Poland ­ Upper Silesia ­ where the recent three decades of economic changes forced the greatest in Poland drop of industrial air pollution and where old steel works, cokeries and coal mines, together with road traffic, are responsible for high concentrations of ambient dust [40, 41, 49]. Investigations were done in a winter heating season, when the emission from combustion of fossil fuels for energy production (especially municipal) causes very high PM concentrations [41, 15]. METHOD The site, selected in Zabrze for the experiment, is representative of the typical air-pollution conditions in the central part of Upper Silesia - by the Directive 2008/50/EC definition [7], it is an urban background measuring point (Fig. 1). The effects of the industrial and municipal emissions on living quarters of the agglomeration are represented and may be observed very well there. Fig. 1. Location of sampling site Ambient dust was sampled with the use of a thirteen stage DEKATI low pressure impactor (DLPI), which collects thirteen PM fractions (0.03-0.06, 0.06-0.108, 0.108-0.17, 0.17-0.26, 0.26-0.4, 0.4-0.65, 0.65-1.0, 1.0-1.6, 1.6-2.5, 2.5-4.4, 4.4-6.8, 6.8-10.0, >10 m) onto thirteen substrate filters. The principle of DLPI operating may be found in [19]. PM was sampled from 26 October 2007 to 22 March 2008 (a whole heating season). A single sample-taking lasted for about one week. The seven thirteen-substrate samples from the period 26 October ­ 27 December 2007 were analyzed for PAH, the remaining seven ones from the period 11 January - 22 March 2008 ­ for the elemental composition. The mass of the dust collected on aluminum (PAH analyzes) and polycarbonate (elemental composition) substrates was determined by weighing the substrates before and after exposure on a Mettler Toledo balance. Before weighing, the substrates were kept in the weighing room for 48 hours (temperature 20±2°C, relative air humidity 48±5%). The concentrations of the fractions of PM were computed from the volume of air passed through the impactor and the masses of the dust collected on its stages. The samples for the PAH analysis, till analyzing, were kept in a refrigerator in tight and lightproof containers. The elemental composition of each of the seven samples of each of the 13 PM fractions from the period 11 January - 22 March 2008 was determined by applying energy dispersive X-ray fluorescence (EDXRF). The ambient concentrations of Cr, Mn, Co, Ni, As, Se, Cd, Pb were determined and the average ambient concentrations (arithmetic means) of each element were computed for each fraction. A PANalytical Epsilon 5 was used. The measurements were done under vacuum, the analysis time for a single sample was 4800 s. The X-ray tube was adjusted depending on a secondary target used: 25 keV and 25 mA for Al, 40 keV and 15 mA for Ti, 40 keV and 15 mA for Fe, 75 keV and 8 mA for Ge, 100keV and 6mA for Zr, 100keV and 6mA for Al2O3. The element concentrations were determined by comparing the results with the calibration curves. Thin-layer single-element Micromatter standards were used to calibrate the apparatus [61]. Weekly measurements of the NIST SRM2873 standards (except for Co, whose recovery was 39%, recoveries of remaining elements were between 91 and 116% of the certified value) and monthly measurements of the monitor were routinely performed to control the quality of the analytical procedure. The detection limits were from 0.2 ng cm-2 for Se to 11.6 ng cm-2 for As. For each of the 13 PM fractions, all its seven samples from the period 26 October - 27 December 2007 were extracted together in dichloromethane (CH2Cl2) in an ultrasonic bath. The extract was percolated, washed and dried by evaporating in the helium atmosphere. The dry residue was diluted in propanol-2 (CH3CH(OH)CH3) and distilled water was added to receive the propanol-2 to water proportion 15/85 (v/v). For selective purification, the resulting samples were solidified (SPE) by extracting in columns filled with octadecyl (C18, Supelco). PAH were eluted with use of dichloromethane (CH2Cl2). The extract of the PAH fraction was condensed in the helium atmosphere to the volume of 0.5 cm3. The samples were analyzed on a Perkin Elmer Clarus 500 gas chromatograph with a flame ionization detector (FID). An RTX-5 Restek capillary 30 m × 0.32 mm × 0.25 m column was used to separate the sample components. The flow of the carrier gas, helium, was 1.5 cm3 min-1. The calibration curves for the 15 PAH standards were used in the quantitative determinations. The linear correlation of the peak surfaces with the PAH concentrations was checked in the concentration range 1­50 ng l-1. The correlation coefficients ranged from 0.95 to 0.99. The time of the whole analysis was 40 min. FID was provided with hydrogen (45 cm3 min-1) and air (450 cm3 min-1). The recoveries of PAH, ranging from 85% to 93%, were determined using a standard containing the 15 PAH. RESULTS AND DISCUSSION The average concentration of PM10 (PM10 = PM1 + PM1-2.5 + PM2.5-10) in the last quarter of 2007 exceeded 46 g m-3, in the first quarter of 2008 ­ 38 g m-3 (Table 1). In most European countries the yearly PM10 concentration has been limited for about twenty years (in Poland since 1998) and its highest permissible value is 40 g m-3. The Table 1. Concentrations of ambient dust (PM, g m-3), and of 15 PAH and 8 elements (ng m-3) related to three fractions of ambient dust in Zabrze, in the central part of Upper Silesia, Poland, in winter PM11) PM PM 4) 5) PM1-2.52) 7.79 7.66 1.11 17.26 <DL 0.04 0.49 <DL 0.27 9.54 0.10 0.05 0.17 0.95 0.28 3.49 4.50 3.57 3.78 2.09 2.41 3.11 0.09 0.36 0.86 PM2.5-103) 5.18 4.98 1.33 20.66 <DL 0.06 0.35 <DL 0.14 7.50 <DL <DL 0.38 0.51 0.25 0.08 0.12 0.05 0.16 0.24 0.27 0.13 <DL <DL <DL 25.55 33.65 2.54 59.99 <DL6) 0.17 2.14 <DL 0.75 23.56 0.19 0.33 1.36 4.07 0.88 15.80 18.03 17.78 17.11 12.84 13.76 16.09 0.73 3.01 6.12 Cr Mn Co Ni As Se Cd Pb Acy Ace F Ph An Fl Py BaA Ch BbF BkF BaP DBA BghiP IP 1) sum of concentrations of dust, element or compound in fractions 0.03-0.06, 0.06-0.108, 0.108­0.17, 0.17­0.26, 0.26­0.4, 0.4­0.65, 0.65­1.0 m 2) sum of concentrations of dust, element or compound in fractions 1.0­1.6, 1.6­2.5 m 3) sum of concentrations of dust, element or compound in fractions 2.5­4.4, 4.4­6.8, 6.8­10.0 m 4) average concentration from 11 January to 22 March 2008 5) average concentration from 26 October to 27 December 2007 6) concentrations below detection limit high PM10 concentrations during a half-year in Zabrze may mean violating this limit. The concentrations of PM2.5 (PM2.5 = PM1 + PM1-2.5) also were high; in the winter 2007/2008 they exceeded the limit 25 g m-3 [7]. PM2.5 and PM1, the fractions of respirable dust, contributed no less than 89 and 72% to PM10, respectively. The average concentrations of the eight toxic elements in Zabrze in the period 11 January ­ 22 March 2008 were low compared to their permissible values both domestic and EU ones, [6,13]. All, except the Cd concentration, were at least 10 times lower than their yearly limits. Because in summer the concentrations of PM and of the PM-related elements are usually lower, their yearly concentrations are not expected to exceed the yearly limits. The concentrations of Co and Se for each PM fraction were very low, lower than their detection limits: 0.1 ng m-3 for Se and 0.2 ng m-3 for Co. In the period 11 January - 22 March 2008, the concentrations of PM1 were high, the eight elements assumed the greatest concentrations as the PM1-related ones (Table 1). In Zabrze all these elements come probably from combustion and occur in PM1 in metal oxides, sulfates and chlorides. The enrichment coefficients [14, 51, 66], presented in Figure 2, confirm the fact. Only EF for PM1-2.5- and for PM2.5-10-related Ni are lower than 10. EF for the rest of the elements are very high, for PM1-related Cr and Mn higher than 100, for As and Pb higher than 1000. It reflects a strong anthropogenic effect on the winter concentrations of these PM-related elements in Zabrze. Seeming not very high compared to the air quality standards, the winter ambient concentrations of the toxic elements in Zabrze are higher than their winter concentrations in other regions of Europe (Table 2). The high concentrations of Pb, Cd, As, the lower than in other regions concentration of Ni (tracer of combustion of oil in typical European urban areas, [65]) and the results from the investigations of the smog episode in Zabrze in January 2006 [41] suggest the combustion of low-quality coal in domestic furnaces (municipal emission) as the source of these elements in Zabrze in winter. 100000 PM1 10000 1000 EFs 100 10 1 Ni Cr Mn As Pb Cd PM1-2.5 PM2.5-10 EFx for the element x is referred to the concentration CSi of Si, a marker element for the Earth crust-EFSi=1 (average Si concenttrations in Zabrze in January­March 2009 were: 122.8 ng m-3 for PM1, 94.9 ng m-3 for PM1-2.5, 172.6 ng m-3 for PM2.5-10). The chemical characterization of the Earth upper continental crust is taken from Wedepohl; 1995 [66] Fig. 2. EF for PM-related elements in Zabrze in winter 2008 Table 2. Ambient concentrations of elements related to various PM fractions at various sites in the world Location As 2.14 2.63 2.98 2 3 6.83 0.3 1.7 2.2 0.6 PM2.5 PM10 0.70 0.2 4.0 4.1 0.3 12.6 9.2 2 5 2.3 1.3 8.4 10.6 1.2 80.5 128.5 3.3 6.9 6.9 49.7 5.5 24.3 1.16 4.98 97.91 24.6 49.8 9 18 12 2.7 10.4 21.5 4 25.6 44.7 4.0 4.6 1.02 3.65 77.25 0.75 2.54 59.99 Cd Cr Mn Ni 0.17 0.21 0.27 17.7 17.3 7 9 3.4 1.59 3.4 3 15.3 15.3 97.8 41.7 PM1 Jan-Mar 2008 PM2.5 PM10 Jan 2006 PM10 PM1 PM2.5 PM2.5 PM2.5 PM2.5 PM2.5 PM10 PM1 PM2.5 PM10 Winter 2002 Winter 2003 Oct-Dec 2003 Jan-Mar 2005 Feb 2006 2005-2006 Nov 2007-Feb 2008 Spring 2009 PM2.5 Sampling period Fraction Concentration, ng·m-3 Pb 23.56 33.1 40.6 184.7 223.6 35 55 54 5.45 5.7 58.5 75.3 17 630.8 420.7 275.8 263.3 Zabrze (Poland); urban background a Zabrze (Poland); urban background [41] Milan (Italy); residential-commercial area [63] Menen (Belgium); suburban/industrial [38] Athens (Greece); suburban [62] Cartagena (Spain); suburban [35] Seoul (Korea); residential [39] Barcelona (Spain); urban background [42] Dehli (India), urban [55] Ulsan (Korea), residential area [25] this study The winter ambient concentrations of total PAH (PAH) in Zabrze were high - the concentrations of PM1- and PM2.5-related PAH were 128.1 ng m-3 and 153.9 ng m-3, respectively. PM1-related PAH were 82% and PM2.5-related PAH were 98% of PM10-related PAH. The concentrations of PM1-related PAH were about 5 times greater than the concentrations of PM1-2.5-related PAH.All PM fractions were rich in 4- and 5-ring PAH, which were no less than 89% of PAH. Among all PM-related PAH, Py, BaAand Ch had the greatest concentrations (PM1-related: 18.03 ng m-3, 17.78 ng m-3, 17.11 ng m-3, respectively). Fl, BbF, BkF, BaP ­ the compounds whose presence and high concentrations in atmospheric air indicate stationary combustion had also great ambient concentrations (12.84­16.09 ng m-3, PM1-related) and contributions to PAH. The proportion CPAH/PAH of the concentration of CPAH (total combustion PAH: Fl, Py, BaA, BbF, BkF, BaP, BeP, IP and BghiP) to the concentration of PAH, expresses the effect of stationary combustion on the PAH concentrations [47, 48, 54]. In Zabrze it was equal to 0.82 for PM1, 0.79 for PM1-2.5 and 0.41 for PM2.5-10- in winter PM1- and PM1-2.5-related PAH come from stationary combustion and PM2.5-10-related PAH ­ from combustion of fuels in car engines [47, 48]. The diagnostic ratios (selected proportions of the concentrations of PAH) for PM1and PM1-2.5-related PAH ([BaA]/([BaA]+[Chry]) equal to 0.51 for PM1 and 0.49 for PM1-2.5 or [BaA]/[BaP] equal to 1.11 for PM1 and 1.15 for PM1-2.5) show that PM1- and PM1-2.5-related PAH came mainly from coal combustion [59,67,68]. According to some authors [26], the winter [BaA]/[BaP] for PM1 and PM1-2.5 in Zabrze are indicative of wood burning. Also [BbF]/[BkF] equal to 0.93, 0.87 and 0.89 for, respectively, PM1, PM1-2.5 and PM2.5-10 suggest wood burning [30]. In turn, the proportions [BaA]/[BaP], [BaA]/([BaA]+[Chry]), [Ph]/([Ph]+[An]) for PM2.5-10-related PAH (0.38, 0.24, 0.67) suggest combustion of gasoline and oil in car engines as the PM2.5-10-related PAH origin [18,26,67] - in winter, at low air temperatures, the gaseous PAH from car engines tend to rapidly condense on big dust particles. The values of [BbF]/[BkF] equal to 0.74, 0.44 and 0.40 for, respectively, PM1, PM1-2.5 and PM2.5-10 suggest the vehicular origin of not only PM2.5-10-related but also of PM1- and PM1-2.5-related PAH in Zabrze in winter [16,47,48,67,68]. In Table 3, the winter concentrations of PM1-, PM2.5- and PM10-related PAH and BaP in Zabrze are compared with the winter concentrations of PAH and BaP at various sites in the world. The wide range of the concentrations of, equally, PAH and BaP is due to the differences in the number of PAH, meteorological conditions, local PAH sources etc. Nevertheless, the greatest concentrations of PM2.5-related BaP and PAH occur in Poland (Zabrze and Bytom, Upper Silesia). In other European cities, at the sites beyond the effect of vehicular and industrial emissions like in Zabrze, the concentrations of PM2.5-related BaP were from 0.33 ng m-3 in Amsterdam (the Netherlands) to 48.00 ng m-3 in Prague, (the Czech Republic) [52]. In Zabrze these concentrations were several times higher. The concentrations of PAH and BaP in Asiatic cities, such as Fashun (China) [21], Delhi (India) [55] and Tiruchirappalli (India) [32], were much greater than in Europe and closer to the winter concentrations in Zabrze. The hazard for humans from an individual ambient PAH is expressed relative to the hazard from BaP, whose toxicity is well characterized as the toxicity equivalency factor (TEF). TEF for BaP is equal to 1, TEF equal to 0 means lack of carcinogenicity of a compound. The hazard from a mixture of PAH is expressed as the BaP equivalent Table 3. Ambient concentrations of BaP and PAH related to various PM fractions at various sites in the world Location Zabrze (Poland), urban backgroundb Bytom (Poland), urban background (T1) [22] Bytom (Poland), city center (T2) [22] Duisburg (Germany), urban background [52] Prague (Czech Republic), urban background [52] Amsterdam (Netherlands), urban background [52] Bangkok (Thailand), urban [37] Atlanta (USA), urban [27] Zagreb (Croatia), urban [57] Fushun (China); urban background [21] Virolahti (Finland), regional background [29] Flanders (Belgium), urban background [64] Rome (Italy), downtown [4] Sampling period Fraction PM1 Concentration, ng·m-3 BaP 16.08 19.19 19.32 6.49 11.12 6.49 19.84 1.05 1.10 3.03 3.15 0.33 1.3 0.27 3.18 3.04 10.71 12.69 0.52 0.69 0.73 1.18 9.9 6.9 0.83 3.2±1.0 6.2±3.9 8.7-24.1 PAHa 128.10 (15) 153.10 (15) 156.11 (15) 85.52(16) 120.69(16) 80.36(16) 128.64(16) 12.63 (32) 15.76 (32) 48.00 (32) 55.11 (32) 7.25 (32) 12.59 (16) 2.86 (28) 21.23 (6) 21.78 (6) 261.82 (13) 334.26 (13) 7.54 (13) 14.53 (13) 13.9 (13) 82.24 (15) 6.70 (14) 7.77 (14) 7.98 (14) 96 (16) 81.5 (16) 11 (11) 32.7±11.8 (13) 75.1±32.7 (13) 136-371.5 (9) Oct ­ Dec 2007 PM2.5 PM10 PM2.5 PM10 PM2.5 PM10 PM2.5 PM10 PM2.5 PM10 PM2.5 PM10 PM2.5 PM2.5 PM10 PM2.5 PM10 PM1 PM2.5 PM10 PM10 PM1 PM2.5 PM10 PM2.5 PM10 PM2.5 PM2.5 PM2.5 Feb ­ Mar 2007 Feb ­ Mar 2007 Sep ­ Nov 2002 Nov 2002 ­ Jan 2003 Jan ­ Mar 2003 Nov 2002 ­ Apr 2003 Oct ­ Dec 2004 Winter 2004 Dec 2004 ­ Feb 2005 Winter 2006 Oct 2006 ­ Mar 2007 Oct 2007 ­ Feb 2008 Dehli (India), urban [55] Augsburg, (Germany) urban aerosol [43] Kaunas (Lithuania), urban [20] Tiruchirappalli (India), urban atmosphere [32] a b Nov 2007 ­ Feb 2008 Feb ­ Mar 2008 location 1 location 2 Winter 2009 Dec 2009 ­ Feb 2010 the number of PAH taken to compute PAH concentration is in parentheses this study (BEQ), which is the sum of the products of the concentrations of individual PAH in the mixture and their TEF [36]. In Zabrze, BEQ for PM2.5 and PM10 were very high in winter (31.70 ng m-3 and 31.81 ng m-3), much higher than in Shanghai (15.77 ng m-3; [10]) or some Japanese cities (BEQ around 2 ng m-3 [58]), where the ambient PAH concentrations were very high. In Zabrze, BEQ for PM1 was 26.73 ng m-3. CONCLUSIONS In Zabrze, in winter, the greatest parts of the PM-related PAH and elements accumulate in the finest PM fractions. The ambient fine particles occur in much greater amounts than coarse particles (PM2.5-10), and the ambient concentrations of the toxic substances they contain, especially carcinogenic PAH, are very high. After penetration into the respiratory system, the finest particles (PM1) reach the pulmonary alveoli where 60-80% of the elements brought with them pass into blood [45]. This is why the toxicity related to PAH [12] and transitive metals [60] is greater for fine than for coarse dust. The correlations between PAH content and cytotoxicity, mutagenity and DNA reactivity are higher for fine than coarse dust [3, 12, 31]. Such high winter concentrations and toxic component content of PM1 cause health hazard for the inhabitants of Zabrze, yet more serious because of its periodic occurrence and several months' duration. ACKNOWLEDGMENTS The work was partially supported by grant No. N N523 564038 from the Polish Ministry of Science and Higher Education.

Journal

Archives of Environmental Protection – de Gruyter

Published: Mar 1, 2013

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