ROCZNIKI GLEBOZNAWCZE TOM LIV NR 3 WARSZAWA 2003: 73-78 TERESA KOZANECKA, KRYSTYNA CZARNOWSKA, AGNIESZKA JAWORSKA CONTENT OF HEAVY METALS IN ROAD COARSE DUST OF WARSAW ENVIRONS W YSTĘPOW ANIE METALI CIĘŻKICH W GRUBYM PYLE DROGOW YM W OKÓŁ W ARSZAW Y Department of Soil Environment Sciences, Division of Soil Science, Warsaw Agricultural University, Warsaw Abstract: The content of Fe, Mn, Zn, Pb, Cu, Ni and Cd was studied in 42 samples of coarse grained road dust from the Warsaw agglomeration environs. The content of heavy metals may be presented in the following diminishing order: Fe > Mn > Zn >Pb > Cu > Ni > Cd. On average, the content of heavy metals was (mg/kg d.m) equal: 600; 134,7; 63,6; 33,8; 30,6; 10,3; 0,69, respectively. Streszczenie: Badano zawartość Fe, Mn, Zn, Pb, Cu, Ni i Cd w grubym pyle drogowym w 42 miejscach aglomeracji warszawskiej. Zawartość metali ciężkich układała się następująco: Fe > Mn > Zn > Pb > Cu > Ni > Cd. Średnie zawartości metali ciężkich wynoszą odpowiednio [mg/kg s.m]: 600; 134,7; 63,6; 33,8; 30,6; 10,3; 0,69. Słowa kluczowe: gruby pył drogowy, metale ciężkie: Fe, Mn, Zn, Pb, Cu, Ni i Cd, zawartość ogółem Key words: coarse road dust, heavy metals: Fe, Mn, Zn, Pb, Cu, Ni, Cd, total content INTRODUCTION The pollution of atmospheric air with communication born dust affects negatively the soils situated at the roadways. The excessive inflow of some chemical compounds and particularly so heavy metals and chlorides leads to malfunction of the natural soil processes. Considering the Warsaw agglomeration and its suburbs only, there have been published several papers confirming the impact [Czarnowska, Konecka-Betley 1979, Czarnowska 1978, Czerwiński 1978, Konecka-Betley et al. 1984, Łakomieć 1984, Czarnowska, Chlibiuk, Kozanecka 2002]. The objective of the present paper was to determine the actual content of Fe, Mn, Zn, Pb, Cu, Ni and Cd in coarse grained road dust sampled from a number of peripheral roads in Warsaw and its environs, within 10 km radius.
74 T. Kozanecka, К. Czarnowska, A. Jaworska MATERIAL AND METHODS In the year 2000 forty two sites were sampled along communication routes of different traffic load. The road dust samples were collected from 10 m long transects situated within the roadway shoulder. Dust samples were first subjected to drying and screening through 1 mm screen. Then, after grinding in agate mill, and exposing to dry mineralization of organic matter at 480-500 C, they were subjected to thermal etching in 20% HC1 under hot environment using the microwave Ethos PLUS Milestone apparatus. In solutions obtained this way, total content of Fe, Mn, Zn, Pb, Cu, Ni and Cd was determined with use of the atom absorption spectroscopic technique (ASA) applying the Perkin-Elmer 2100 apparatus. The analytical data have been subjected to statistical analyses. RESULTS AND DISCUSSION The concentration of iron in the road dust did not exceed the level typical of the geochemical background [Czarnowska 1996] and it varied within 0.30 to 0.86%, reaching an average value of 0.60%. Relatively smallest concentration of Fe in road dust was found near roads characteristic of moderately intensive traffic (Table 1, item 21 and 26); it was the highest in dust collected from roads located along the European transit routes E-71 and E-30 (Table 1, items 32, 42). The concentration of iron in street dust from Warsaw was 2.46% on average and it was significantly higher comparing with that concentration found in road dust. A significantly positive correlation was found between iron content and nickel and zinc content (Table 3). The actually low value of correlation coefficient shows the low level of iron content variability in the road dust (Table 2). The concentration of manganese in the studied road dust was 134.7 mg/kg d.w. on average, and it was significantly smaller from the geochemical background, with its 289.0 mg/kg d.w. average content [Czarnowska 1996]. The concentration of manganese in Warsaw street dust, equal 115.1 mg/kg d.w., was lower than in the road dust [Czarnowska, Bednarz 2000]. The concentration of manganese in street dust and road dust depends mainly on its amount in the soils situated near the communication routes. The Warsaw agglomeration soils have not been contaminated with manganese, as well [Czarnowska 1978]. The Pearsons correlation coefficient detects significantly positive correlation between manganese and nickel only (Table 3). The content of zinc has varied in the studied dust from 13 to 173 mg/kg d.w. (63.6 mg/kg d.w. on average - Tables 1 and 2). The highest concentration of the element was recorded in several objects (items 6, 7, 14, 19, 30, 35, 36, 39, 40, Table 1). The concentration of zinc in those objects was from 3.3 to 5.7 times higher than in the uncontaminated soils. On the other hand, however, the average Zn content in road dust was 1.23 times smaller than that in the arable soils situated near the roads [Czarnowska, Chlibiuk, Kozanecka 2002].
Content o f heavy metals in road coarse dust o f Warsaw environs 75 TABLE 1. Total content of heavy metals in the road dusts TABELA 1. Ogólna zawartość metali ciężkich w pyle drogowym Lp. Locality - Lokalizacja Fe [%] Mn Jzn IPb I Cu INi le d [mg/kg s.m. -d.w.l 1 WARSZAWA, ul. Wał Miedzeszyński 596 0.69 131 43 18 19 12.0 0.70 2 WARSZAWA, ul. Wał Miedzeszyński 196 0.51 77 32 31 27 6.4 0.54 3 JÓZEFÓW, ul. Rakietowa 0.44 54 26 12 15 5.4 0.48 4 JÓZEFÓW, ul. Nadwiślańska 70 0.39 63 34 20 10 5.4 0.84 5 OSTROWIK [171 0.43 76 23 30 12 6.8 0.62 6 W ESOŁA przed Sulejówkiem, ul. Trakt Brzeski 77 0.76 161 134 40 21 22.4 1.22 7 KONflK STARY Гtrasa 21 0.72 99 173 63 25 10.0 0.82 8 WARSZAWA - obwodnica kierunek Radzymin 0.76 178 89 32 30 12.2 0.92 9 NIEPORĘT 0.59 112 47 29 29 8.2 0.76 10 ZALEW ZEGRZYŃSKI 0.39 106 16 13 8 5.0 0.68 11 ZEGRZE płd. - Legionowo [trasa 111 0.68 165 64 46 23 9.6 0.90 12 LEGIONOWO I [ trasa 111 0.76 99 44 31 52 8.6 0.74 13 LEGIONOWO II [trasa 111 0.66 128 79 47 73 7.2 0.86 14 JABŁONNA, teren Pałacu PAN 0.72 129 120 40 72 9.4 1.44 15 BIAŁOŁĘKA, ul. Modlińska 0.69 122 72 46 47 10.6 0.90 16 WILANÓW, ul. Przyczółkowa/Karuzeli 0.41 126 31 13 10 9.0 1.48 17 KONSTANCIN JEZIORNA, ul. Warszawska 0.46 87 48 15 25 7.8 0.96 18 CHYLICZKI, ul. Chyliczkowska 0.40 86 13 13 7 5.4 0.68 19 PIASECZNO, ul. Puławska/Chyliczkowska [7231 0.52 86 39 23 84 9.0 0.76 20 STARA IWICZNA 0.63 113 21 21 31 8.6 0.84 21 LESZNOW OLA 0.30 51 40 23 3 4.2 0.76 22 W arszaw a-t R A SA KATOWICKA, Al. Krakowska 0.63 159 77 38 24 11.0 1.14 23 JANKI, Al. Krakowska 0.75 208 41 26 14 13.0 1.24 24 RASZYN, Al. Krakowska, przystanek autobusowy 0.73 132 63 39 31 11.6 1.06 25 W arszaw a-pia SECZN O 0.78 160 63 29 21 15.2 1.08 26 MAGDALENKA 0.33 97 31 35 9 7.8 0.76 27 SEKOCIN [E-771 0.58 107 38 25 18 9.2 0.86 28 NADARZYN 0.48 147 30 30 11 7.4 0.80 29 WŁOCHY 0.67 149 77 33 38 12.0 0.98 30 OŻARÓW [E-301 0.77 158 101 35 75 13.8 1.18 31 BŁONIE, ul. Poniatowska 0.77 151 51 36 22 12.4 2.16 32 ŁOMIANKI, ul. Stary Tor [E-771 0.79 144 57 32 31 15.8 1.24 33 WOLICA [E-671 0.67 107 38 23 33 11.6 1.02 34 OTREBUSY 0.52 103 31 23 39 10.0 0.96 35 PIASTÓW, Zakłady Akumulatorowe 0.58 98 138 108 24 9.0 1.32 36 PRUSZKÓW 0.64 95 122 37 64 8.2 0.92 37 UFISUS, ul. Ryżowa 0.60 145 81 32 37 12.2 1.10 38 ŚWIECICE [E-301 0.66 148 79 124 67 12.4 1.02 39 BRWINÓW 0.52 206 132 26 24 18.2 1.36 40 PIEŃKÓW, stacja benzynowa 0.80 329 127 40 35 19.0 1.08 41 ŁOMNA, Trasa Gdańska IE-771 0.48 400 31 16 13 8.4 0.80 42 OŁTARZEW, ul. Poznańska [E-301 0.86 166 75 39 32 11.8 1.12 Uncontaminated soils (geochemical background) Gleby niezanieczyszczone (tło geochemićzne) 1.29 289 30 9.8 7.1 10.2 0.18
76 T. Kozcinecka, К. Czarnowska, A. Jaworska TABLE 2. Statistical assessment of heavy metals content [mg/kg d.w.] TABELA 2. Statystyczna ocena wyników zawartości metali ciężkich [mg/kg s.m.] Element Pierwiastek Range Zakres Mean Średnie Standard deviation Odchylenie standard. Fe 300-860 600 140 24.08 Mn 81-400 134.1 64.36 47.78 Zn 13-173 63.60 39.07 61.44 Pb 12-124 33.85 21.69 64.08 Cu 3-84 30.60 20.49 66.98 Ni 4.2-22.4 10.31 3.84 37.30 Cd 0.48-2.16 0.67 0.30 30.69 Coefficient of variation Współczyn. zmienności m Skłodowski et al. [1995] have found many times higher zinc concentration in dry deposit in not built up areas (160-710 mg/m2). These last mentioned results are, however, not comparable because of the methodological incompatibility. It may be concluded from the statistical analyses that the zinc content has been positively correlated with the concentration of lead and nickel (Table 3). The concentration of lead in road dust has ranged within 12 to 124 mg/kg d.w. (33.85 mg/kg d.w. on average). The highest concentration of Pb in road dust was recorded in road dust collected at the battery plants in Piastów and at the international communication route E-30 (Table 1, items 35 and 38). Smaller concentration of Pb (below 15 mg/kg) was found in road dust of roadways characteristic of smaller traffic load (Table 1, items 3, 10, 16, 17, 18). The mean concentration of lead in the studied dust was 2.3 times smaller comparing the Warsaw agglomeration street dust. It should be noticed that the road dust contained a bigger admixture of soil than the street dust. Paukszto et al. [1998] have found bigger amounts of Pb in dust deposited in the vicinity of gasoline stations - reaching the average level of 345 mg/kg. TABLE 3. Pearson s correlation coefficient (r) for particular pairs of heavy metals content TABELA 3. Współczynniki korelacji Pearsona (poziom istotności 0,05) między zawartością metali ciężkich Element R Pierwiastek Fe-Zn 0.516 Fe-Ni 0.677 M n-ni 0.530 Zn-Pb 0.553 Zn-N i 0.561 Pb-Zn 0.553 Ni-M n 0.530 Cd-Ni 0.535 It can be concluded from the statistical analyses that the content of lead has been positively correlated with the content of zinc only (Table 3). The content of copper in road dust has varied from 3 to 84 mg/kg d.w. (reaching the average level of 0.60 mg/kg d.w.). The difference between highest and smallest concentration of Cu was 28 and it was much more higher than in the road dust of Warsaw agglomeration [Czarnowska, Bednarz 2000]. Noteworthy, the highest concentration of copper in road dust was found either near trolley-bus or tram traction or along different roads
Content o f heavy metals in road coarse dust o f Warsaw environs 77 (Table 1, items 12, 13, 14, 19,30, 36,38). The dust collected from roads of little traffic load contained little copper (Table 1, items 10, 18, 21, 26). The content of Cu in the studied road dust did not show any correlation with any metal considered similarly as it was considering the Warsaw agglomeration dust [Czarnowska, Bednarz 2000]. It can be concluded from the stiidy by Skłodowski et al. [1995] that the concentration of Cu in dry deposition from the rural area ranged from 53 to 150 mg/m2, while that in the town dust varied from 48 to 612 mg/m2. The average content of nickel in road dust was 10.31 mg/kg d.w. (and was equal the geochemical background) which meant more than three times lesser as compared with the Warsaw agglomeration street dust. The highest nickel concentration was found in road dust collected from the town of Wesoła (22.4 mg/kg d.w.), somewhat lesser was that from Brwinów and Pieńków ( 18.2 and 19.0 mg/kg d.w., respectively). The values of Pearsons correlation coefficient suggest the significantly positive correlation between nickel concentration and manganese concentration (Table 3). The content of cadmium in road dust varied from 0.48 to 2.16 mg/kg d.w. (Tables 1 and 2). Mean concentration of the element in the studied dust was maintained at the same level as that in Warsaw agglomeration street dust but it was 1.76 times higher compared with the A horizon of the arable soils situated near the highways [Czarnowska, Chlibiuk, Kozanecka 2002]. In 17 samples analyzed the concentration of Cd has exceeded the level of 1 mg/kg d.w., and in one case it was as high as 2.16 mg/kg d.w. (Table 1, item 32). Relatively least Cd content was found in the dust samples collected from roads characteristic of poor traffic (Table 1, items 2 and 3). The content of cadmium in road dust has been significantly correlated with the concentration of nickel only. The value of correlation coefficient was rather low: 30.69%. This value suggests the rather little differentiation in cadmium content in samples from road dust. It can be concluded from earlier studies.conducted in Warsaw and its environs that Cd accumulation in the superficial layers of soil had been the result of different pollutants of atmospheric air, including also the communication (traffic) pollution [Czarnowska 1978a, b]. CONCLUSION 1. The average concentration of heavy metals [mg/kg d.w.] in road dust may be presented in the following descending order: Fe (600.0) > Mn ( 134.7) > Zn (63.6) > Pb (33.8) > Cu (30.6) >Ni (10.3) > Cd (0.67) 2. The average concentration of zinc, lead, copper, nickel and cadmium in the road dust was above the level of the geochemical background while that of iron and manganese was significantly lower than the background reference value. 3. The actual concentration of zinc, lead, copper, cadmium and nickel in the road dust depended on several factors: traffic intensity, actual distance from the tram and trolley-bus traction as well as the concentration of the elements in the soils along the communication routes.
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