Badania mobilnych frakcji metali w opadzie pyłowym i możliwość migracji metali do gleby

126 JAN KALEMBKIEWICZ, EL¯BIETA SITARZ-PALCZAK, ELEONORA SOÈO, DANUTA NOWAK, IRENA TROJNAR

http://www.degruyter.com/view/j/ssa (Read content)

SOIL SCIENCE ANNUAL

Vol. 65 No. 3/2014: 126–129

INTRODUCTION

Natural and anthropogenic air pollutants and their migration in the form of precipitation into the soil are a problem, since they can be transported in the atmosphere over long distances from their place of origin (Harrison et al. 2001; Varga et al. 2013). The source of the metals are mainly particulate pollution air falling by gravity (settling dry), or by rinsing with air by rain (settling wet) which are referred to a shipment of metal (kg·km–2_{) into the soil. Dust particles}

are able to modify the properties of the soil. The emissions of metals and their compounds by industrial plants, in the wake of the dry and wet deposition processes, give rise to migration of metals to the soil environment. The migration of metals in soil depend on the chemical forms of heavy metals present in dustfall. The evaluation of migration mechanism is possible by knowing the functional speciation of metals in dust. The form of heavy metal depends on the source of a given dust. The most common forms containing metals are bound to organic matter fraction, fraction associated with Fe and Mn oxides and residual, in urban street dusts (Banerjee 2003; Wang et al. 1998); carbonates, oxides and reducible fraction, oxidisable and sulphidic fraction, or residual fraction in fine urban particles (Fernández et al. 2002). The main fractions of metals in dust can also be: exchangeable and carbonate-associated fractions and residual in urban dust fallout in an industrial area (Li et al. 2013).

The results of long-term precipitation measurements of pollutants (monthly, quarterly, and annual periods) are the basis for the assessment of pollution trends on the covered areas (Cercasov and Wulfmeyer 2007). Variation characteristics of particulate matter and its composition are particularly observed in urban areas (Adachi and Tainosho 2004; Park et al. 2007). The impact of weather conditions and time of year on the size and degree of fluctuation in the particulate matter was also confirmed (Vassilakos et al. 2006). The results of the monitoring do not allow us to fully assess the supply of metals from soil powdered fallout. Metal mo-bility is particularly difficult to assess, although the presence of metals in dustfall is confirmed, and the volume of dustfall vary (website 1).

The objective of the present study was to assess the possible deposition of metals from dustfall into the soil, to research the physico-chemical properties and mobility fractions of dustfall, and to study the possible migration of metals into the solutions.

MATERIALS AND METHODS

The object of study was the dustfall stored on the laboratory position in the town of Rzeszów (Powstañ-ców Warszawy Ave. 6, Poland). The samples were collected at a height of approx. 15 meters from the ground surface in the 3-month period (quarterly periods between 2011 and 2012). Depending on the time of year the samples were in a form of liquid (settling JAN KALEMBKIEWICZ*, EL¯BIETA SITARZ-PALCZAK, ELEONORA SOÈO,

DANUTA NOWAK, IRENA TROJNAR

Rzeszow University of Technology, Faculty of Chemistry, Department of Inorganic and Analytical Chemistry, Powstañców Warszawy Ave. 6, 35-959 Rzeszów, Poland

Mobile fractions in dustfall and possible migration of metals to soil

Abstract: The atmospheric fallout over the Rzeszów town was investigated. Intensity of dustfall (quarterly periods, 2011–2012) and its physicochemical properties (acid-base character, solubility and sequential solubility, mobile fractions) were investigated. The intensity of dustfall was variable from 25 to 83 g·m–2 _{and depended on the season. Contents of metals in precipitation were diverse} with quantities exceeding 1%: Fe, K, Ca, Na, in 0.1–1%: Mg, Zn, Na, Ca, Mn, Ni, Co, Cr, and less than 0.1%: Cu, Bi, Cr, Mn, Ni, Pb. It was found that the dustfall is a possible source of metals. The atmospheric fallout can enlarge a pool of metals in soils from 0.18% up to 80%.

127 Mobile fractions in dustfall and possible migration of metals to soil

wet) or solid (settling dry). Liquid samples were subjected to evaporation and drying (T£100°C) to constant weight, followed by trituration (j£0.3 mm). Solid samples were treated by distilled water (in order to obtain comparable reference state) and further proceeding was the same as the liquid sample. Po-tential sources of particulate pollutants studied, regardless of dust transported with the wind could be local power plants, households, construction sites and transport traffic. The collected material was analyzed in the laboratory. A dustfall intensity, the nature of the acid-alkaline water (pH=7), water solubility and mobility of 14 metals (Na, K, Mg, Ca, Fe, Mn, Ni, Cr, Pb, Cd, Zn, Cu, Co, Bi) depending on the pH were analyzed. The analytical process involved direct carrying components of dustfall to the aqueous solutions (pH 7, 5, 3) of nitric acid(V) by sequential extraction, or by fusion with soda or solubilization in a mixture of concentrated HNO₃ (65%)/HClO₄ (70%) (3:1) and the determination of metal solutions by flame atomic absorption spectrometry (FAAS). The results were calculated on the equivalents of dry weight of the dustfall. The analytical work used: atomic absorption spectrometer PERKIN ELMER 3100, analyzer Elementar Vario ELIII Analysensysteme GmbH, moisture analyzer MAX50/1 Radwag, sequential extraction kit and equipment (platinum) for special markings. Dates of dustfall collection and set of its physico-chemical properties are given in Table 1.

RESULTS AND DISCUSSION

The intensity of the pulverized solid precipitation varied from 25.3 to 82.6 g·m–2 _{depending on the time}

of sampling (Table 1). The highest intensity of dustfall was 82.6 g·m–2_{, which was recorded in the first quarter}

of 2011. In the corresponding period in the following year (the I quarter of 2012) dustfall intensity was

significantly lower and amounted to 54.1 g·m–2_{. Low}

intensity (25–26 g·m–2_{) of solid precipitation was}

observed in the third and fourth quarter of 2012. Correlation was found between the amount of rain and the season. The results indicate an increased dust deposits (1.5–2 times) during periods of winter-spring compared to other seasons.

The dustfall showed predominantly weakly acidic reaction, with the exception of periods spring and summer, when it was basic or close to neutral (Table 1). This fact probably resulted from burning of sulfur-containing coals burned in households (autumn-winter periods), and the and the presence of alkali metal compounds, mainly in calcium dust from construction (spring-summer periods). Studies show that fall of 1 kg acidified or alkalized pollutants in quarter enters to the environment or causes loss to 0.0012 moles of hydrogen ions.

Solubility (at 25°C) of dust in aqueous solution varied from 0.090 to 0.158 g per 100 g of H₂O (Table 1). Dust was characterized by a variable content of soluble fraction in aqueous solution from 18 to 31.5% by its weight. Insoluble fraction of dust changed respectively from 68.5 to 82%. A significant effect of pH on the solubility of the dust was in the range of 3–7 (similar to the environmental conditions). The increase in pH of the aqueous solution from 3 to 5 induced a decrease in the solubility of the dust of approximately 8–16%, a further increase in pH from 5 to 7 decrease its solubility for a further 6–7%. There was no correlation between time of sampling and the solubility of dustfall. The results showed that the mobile part of the dustfall is variable in time, and evaluation is possible only through experimental studies because of the variable nature and composition of the dustfall as a consequence of the variable sources of emission (natural, anthro-pogenic).

Dustfall typically contained metals in the form of macroelements and trace elements (Table 2), and the metal content of the dustfall has changed in the investigated seasons. Examples are sodium and calcium, which content in dustfall was lower in periods I–IV of 2011 (5.7–21.6 g Na·kg–1_{, 1.6–9.1 g Ca·kg}–1₎

in relation to the seasons I–IV of 2012 (10.7–22.2 g Na·kg–1_{, 8.9–12.3 g Ca·kg}–1_{), as well as zinc and copper}

contents of up to 1600 mg Zn·kg–1 _{and 100 mg Cu·kg}–1

in periods I–IV of 2011, and 1400–5100 mg Zn·kg–1

(Cu 100–260 mg·kg–1_{) in the periods I–IV of 2012.}

The contents of heavy metals in dustfall, despite the seasonal fluctuations, were comparable with the concentration of this metals in city dust in other cites: Hong Kong (Wang et al. 1998), Aviles in Spain (Ordonez et al. 2003), Istambul in Turkey (Al-Kha-shman 2004), and Zielona Góra in Poland (Walczak

TABLE 1. Intensity of dustfall and the properties of dusts g n il p m a S , d o ir e p ,r e tr a u q r a e y ll a ft s u D y ti s n e t n i m · g ( –2₎ H p 1 _Chemcial r e t c a r a h c ll a ft s u d f o y til i b u l o S g 0 0 1 (· g H2O)–1 f o n o it c a r F 7 H p ,ll a ft s u d el b u l o s insolubel ) % ( 1 1 0 2 ,I 1 1 0 2 ,I I 1 1 0 2 ,I II 1 1 0 2 , V I 2 1 0 2 ,I 2 1 0 2 ,I I 2 1 0 2 ,I II 2 1 0 2 , V I 6 . 2 8 8 . 2 4 7 . 1 3 5 . 0 3 1 . 4 5 5 . 2 3 3 . 5 2 0 . 6 2 4 5 . 6 6 4 . 7 6 5 . 7 5 5 . 6 0 8 . 6 0 2 . 7 5 7 . 6 0 1 . 6 A2 B3 B A B A A A 8 5 1 . 0 5 9 0 . 0 3 1 1 . 0 0 9 0 . 0 2 1 1 . 0 5 1 1 . 0 2 0 1 . 0 2 3 1 . 0 5 . 1 3 1 . 9 1 6 , 2 2 0 . 8 1 4 . 2 2 0 . 3 2 4 . 0 2 4 . 6 2 5 . 8 6 9 . 0 8 4 . 7 7 0 . 2 8 6 . 7 7 0 . 7 7 6 . 9 7 6 . 3 7 1 _{pH of water solution of dustfall (initial pH of water 7.02)} 2 _{A – acidic character of dustfall}

128 JAN KALEMBKIEWICZ, EL¯BIETA SITARZ-PALCZAK, ELEONORA SOÈO, DANUTA NOWAK, IRENA TROJNAR

2010). Mobile fraction of metals in dustfall in comparison with their total content varied widely. Mobile fractions of metals (pH=7) create a series of: 0.12% Fe <11% Zn <16% Bi, Cr <20% Cu <25% Mn <27% Pb <33% Co <59% Ni, and 37–81% Ca, 19–80% Na, 10–33% K and 22–81% Mg. Wide range of changes of mobile fraction of individual metals indicate a variety of emission sources and the lack of a clear effect of the seasons on the content of the mobile fraction of metals in dustfall.

Metal load carried by the fallout (g·m–2_{) depend}

on the date of sampling (Table 3). The highest load was typical for iron, suitably from 0.4 g·m–2 _{(the III}

quarter of 2011) to 2.0 g·m–2 _{(the IV quarter of 2012).}

It was also found, that sodium load – from 0.24 g·m–2

(the IV quarter of 2011) to 1.8 g·m–2 _{(the I quarter of}

2011) and calcium load – from 0.013 g·m–2 _{(the IV}

quarter of 2011) to 0.18 g·m–2 _{(the I quarter of 2012)}

was high. Low intensity of precipitation in the form of particulate matter was typical for chrome – up to 18.1 mg·m–2 _{(the I quarter of 2012), lead – up to 22.1}

mg·m–2 _{(the I quarter of 2012), and nickel – up to}

13.8 mg·m–2 _{(the I quarter of 2011).}

The dustfall can be a source of uncontrolled supply of metal to the soil. The chemical nature of the dustfall (acid, alkaline), as well as diverse solubility of dustfall can have influence on the physico-chemical properties of surface levels of soil. The dusts that got to the soil can change the chemical composition of the soil, change its pH, and decrease its biological activity, and cause

the mobilization of metals in the environment. Mobile fractions of heavy metals involved in food chain can be particularly dangerous. The effect of the accumulation of metals in the soil can be reduced the sorption capacity of soil.

CONCLUSIONS

1. The intensity of dustfall in Rzeszów in the period 2011–2012 varied from 25 to 83 g·m–2 _{and depended}

on the season. Dusts with acidic reaction predo-minated.

2. A typical feature of the dustfall was a significant percentage (18–32.5%) of fraction soluble in water. Alkalinization of the solution caused a significant immobilization of the soluble fraction of dustfall. 3. The dustfall showed a varied content of metals. Over a three month period high amounts of Fe (0.4– 2.0 g·m–2_{), Ca (0.013–0.18 g·m}–2_{) and Na (0.24–}

1.8 g·m–2_{) were observed, while metals such as Ni,}

Cr, and Pb have shown lower concentrations – up to 14 mg·m–2_{, up to 18 mg·m}–2 _{and up to 22 mg·m}–2_,

respectively.

4. Mobile fractions of metals in dustfall were variable and comprise from 0.18% (Fe) to 80% (Ca, Na, Mg), in reference of their total contents. Wide range of changes of mobile fraction of individual metals in dustfall indicate a variety of emission sources and the lack of a clear effect of season on its content.

TABLE 2. Content and mobility of metals in dustfall l a t e M Invesitgaitonpeirod,quatre,ryear t n e t n o c l a t o T Mobiel rfaciton,pH7 1 1 0 2 V I – I I–IV2012 I–IV2011 I–IV2012 g k · g ( st n e m el e o r c a M –1₎ a N 1 K g M a C 6 . 1 2 – 7 . 5 9 4 – 5 . 2 1 7 . 2 – 4 . 1 1 . 9 – 6 . 1 2 . 2 2 – 7 . 0 1 0 . 1 2 – 5 . 4 1 0 . 3 – 1 . 2 3 . 2 1 – 9 . 8 2 . 7 1 – 2 . 1 0 . 4 1 – 1 . 2 7 . 0 – 4 3 . 0 7 . 4 – 5 . 1 5 . 5 1 – 6 . 2 4 . 5 – 1 . 2 7 . 1 – 6 . 0 7 . 5 – 4 . 3 g k · g m ( st n e m el e e c a r T –1₎ n Z u C n M e F r C i N o C b P i B d C 0 0 6 1 – 0 0 6 0 0 1 – 0 6 0 6 3 – 0 0 3 0 0 5 1 5 – 0 0 6 3 2 0 8 2 – 0 2 2 0 0 5 – 0 8 0 8 1 – 0 6 0 4 4 – 0 4 3 0 0 7 – 0 2 1 0 2 < 0 0 1 5 – 0 0 4 1 0 6 2 – 0 0 1 0 0 4 – 0 8 2 0 0 2 5 – 0 0 2 2 0 0 4 – 0 0 3 0 0 1 – 0 4 0 8 – 0 6 0 0 7 – 0 0 3 0 2 1 – 0 0 1 .l . d 0 8 1 < 0 2 < 0 4 < 0 6 < 0 2 < 0 8 2 < 0 6 < 0 2 1 – 0 6 0 0 2 – 9 8 .l . d 0 2 1 < 0 2 < 0 0 1 – 0 2 0 6 – 0 4 0 6 < .l . d .l . d 0 0 1 – 0 8 0 8 .l . d d.l. – detection limit.

1_{analyzed after the digestion of samples in the mixture of concentrated}

acids HNO3 and HClO4 in the ratio of 3:1.

TABLE 3. Metal load carried by the fallout

d.l. – detection limit.

1_{analyzed after the digestion of sample in the mixture of concentrated}

acids HNO3 and HClO4 in the ratio of 3:1. l a t e M Invesitgaitonpeirod,quatre,ryear 1 1 0 2 II – I III–IV2011 I–II2012 III–IV2012 m · g ( st n e m el e o r c a M –2₎ a N 1 K g M a C 8 . 1 – 6 2 . 0 0 . 4 – 7 6 . 0 5 4 0 . 0 – 0 2 0 . 0 6 6 0 . 0 – 3 2 0 . 0 4 3 . 0 – 4 2 . 0 9 5 . 0 – 8 3 . 0 2 3 0 . 0 – 8 1 0 . 0 2 4 0 . 0 – 3 1 0 . 0 4 7 . 0 – 5 3 . 0 0 8 . 0 – 8 3 . 0 3 1 . 0 – 9 1 0 . 0 8 1 . 0 – 3 3 0 . 0 4 7 . 0 – 7 2 . 0 4 5 . 0 – 6 3 . 0 6 7 0 0 – 5 5 0 . 0 4 1 1 . 0 – 0 1 0 . 0 m · g m ( st n e m el e e c a r T –2₎ n Z u C n M e F r C i N o C b P i B d C 3 . 0 3 – 6 . 8 7 7 . 2 – 7 8 . 0 9 . 9 – 3 . 4 3 2 1 1 – 6 . 3 3 7 1 . 7 – 3 1 . 3 8 . 3 1 – 7 2 . 6 7 9 . 4 – 7 2 . 2 1 . 2 1 – 3 8 . 4 6 . 7 1 – 3 8 . 8 6 . 0 < 7 . 8 4 – 1 . 3 1 3 0 . 3 – 3 8 . 0 7 . 9 – 8 . 3 8 6 5 1 – 7 6 3 3 5 . 8 – 3 3 . 2 3 6 . 4 – 3 4 . 2 3 8 . 1 – 7 . 1 0 . 1 1 – 8 . 3 4 . 7 – 7 . 3 2 . 0 < 3 4 1 – 2 . 0 7 0 . 6 – 9 . 3 1 . 9 1 – 1 . 9 4 4 9 1 – 4 1 7 1 . 8 1 – 3 7 . 9 6 . 2 – 0 . 2 0 . 3 – 6 . 2 1 . 2 2 – 3 7 . 9 0 . 6 – 9 . 3 .l . d 8 2 1 – 3 . 6 3 7 5 . 6 – 0 6 . 2 4 . 0 1 – 1 . 9 9 4 3 1 – 2 6 2 1 1 . 0 1 – 7 8 . 9 0 6 . 2 – 3 5 . 2 3 0 . 2 – 7 5 . 1 2 . 8 1 – 1 . 0 1 6 . 2 – 5 . 2 .l . d

129 Mobile fractions in dustfall and possible migration of metals to soil

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indu-Badania mobilnych frakcji metali w opadzie py³owym

i mo¿liwoœæ migracji metali do gleby

Streszczenie. Poddano badaniom sta³y opad atmosferyczny nad miastem Rzeszowem. Badano intensywnoœæ opadu py³owego (okresy kwartalne w latach 2011–2012) i jego w³aœciwoœci fizykochemiczne (charakter kwasowo-zasadowy, rozpuszczalnoœæ i roz-puszczalnoœæ sekwencyjn¹, mobilnoœæ frakcji). Intensywnoœæ opadu py³owego by³a zmienna: od 25 do 83 g·m–2 _{na kwarta³ i zale¿a³a} od pory roku. Stwierdzono dominuj¹cy charakter kwasowy opadu z wyj¹tkiem okresów wiosenno-letnich oraz znacz¹cy udzia³ frakcji rozpuszczalnej (18–31,5%) w opadzie (pH 7). Analizowano zawartoœci metali w opadzie i stwierdzono, ¿e wystêpowa³y w iloœciach powy¿ej 1%: Fe, K, Ca, Na, w zakresie 0,1–1%: Mg, Zn, Na, Ca, Mn, Ni, Co, Cr oraz poni¿ej 0,1%: Cu, Bi, Cr, Mn, Ni. Stwierdzono, ¿e sta³y opad mo¿e byæ istotnym Ÿród³em metali migruj¹cych w zró¿nicowanym stopniu (od 0,18% do 80% ich ca³ko-witej zawartoœci w opadzie) do gleby.

S³owa kluczowe: py³owy opad atmosferyczny, zanieczyszczenia, metale, mobilnoœæ

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website 1: http://www.wios.rzeszow.pl/pl/1,60,170/2/raporty.html (WIOŒ Rzeszów, Report on the state of the environment in the Podkarpackie region in 2012).

Received: October 7, 2014 Accepted: December 17, 2014