Determination of major natural and anthropogenic source profiles for particulate matter and trace elements in Izmir, Turkey

Available online at www.sciencedirect.com

Chemosphere 71 (2008) 685–696 www.elsevier.com/locate/chemosphere

Determination of major natural and anthropogenic source profiles for particulate matter and trace elements in Izmir, Turkey Sinan Yatkin *, Abdurrahman Bayram Dokuz Eylul University, Faculty of Engineering, Department of Environmental Engineering, Kaynaklar Campus, 35160 Buca, Izmir, Turkey Received 9 April 2007; received in revised form 25 October 2007; accepted 26 October 2007 Available online 20 February 2008

Abstract Samples of PM10 and PM2.5 were collected from several natural and anthropogenic sources using in-stack cyclone, grab sampling/ resuspension chamber and ambient air samplers. The chemical characterization of the samples was achieved containing Al, Ba, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Sr, V and Zn using an inductively coupled plasma-optical emission spectrometer (ICPOES). The elemental fractions (weight percent by mass), standard deviations and uncertainties were reported. The elemental compositions of PM emitted from mineral industries and cement kiln were dominated by terrestrial elements, particularly Ca, whereas the profile of top-soil mainly contained Al and Ca. The profiles of industrial sources were generally typical for related ones; however, significant differences were obtained for some of them. Similarly, the profiles of fuel burning emissions have significant differences compared to profiles obtained all around the world. Ó 2007 Elsevier Ltd. All rights reserved. Keywords: PM10; PM2.5; Elemental profile of sources; Izmir

1. Introduction The elemental contents of PM emitted from the sources are one of the main data used in the source/receptor based models. For the chemical mass balance (CMB) model, the fractional abundances of species in PM emitted from the sources with their uncertainties are used as input data (Watson et al., 2001; USEPA, 2002). Since, the elemental compositions of several sources were identified in data base of USEPA (SPECIATE) and studies (Watson and Chow, 2001; Watson et al., 2001; Ho et al., 2003; Chow et al., 2004), it is recommended to characterize the PM sources locally for source apportionment studies (Paode et al., 1999). Besides, the profiles of some sources such as top-soil, coal burning emissions and biomass emissions, etc., differed significantly with respect to the geographical locations (Watson and Chow, 2001; Watson et al., 2001; Ho et al., 2003; Chow et al., 2004). The PM10 and PM2.5 (aero*

Corresponding author. Tel.: +90 232 4127133; fax: +90 232 4530922. E-mail address: [email protected] (S. Yatkin).

0045-6535/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.chemosphere.2007.10.070

dynamic diameter is equal or less than 10 and 2.5 lm, respectively) are the most characterized PM fractions in these studies, since source apportionment studies of ambient PM concentrations are focused to these fractions. Since several studies on atmospheric PM and elemental concentrations have been performed for many years in Turkey (Karakas and Tuncel, 1997; Gullu et al., 2000; Yatin et al., 2000; Odabasi et al., 2002; Yatkin and Bayram, 2005), there is no study on source characterization in terms of elemental content of PM fractions. The aim of this study is to characterize major and minor sources of PM containing top-soil, marine salt, cement industry, ceramic industry, asphalt plant, mineral industries (area source includes stone quarries, lime kiln, asphalt plants, and concrete plants), wood burning, olive oil residual (OOR) burning, coal (lignite) burning, fuel oil #4 burning, natural gas burning power plant (Aliaga PP) located in a highly polluted industrial area, coal burning power plant, electric arc furnace of steel production from scrap (EAF-Steel), slag of these furnaces, lead recovery furnace from car batteries, bell metal casting, rim production from aluminum, tobacco

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processing and traffic emissions in Izmir area. These data were used in source apportionment of PM using factor analysis (Yatkin and Bayram, 2007), positive matrix factorization and CMB models (Yatkin, 2006). 2. Materials and method 2.1. Sampling site In this study, Izmir, which is the third largest city in Turkey with nearly three million inhabitants, was the study area. Izmir is located at the coast of Aegean Sea and surrounded by relatively high mountains (500–1000 m). There are many industrial activities in the industrial zones located in the city and nearby. The main industries in these zones are cement, ceramic, stone quarries, automotive, food and chemical industries, etc. Also, one of the biggest industrial regions of Turkey including a petroleum refinery, petrochemical complex, and several EAF-Steels is located at 50 km north of the city. Fossil fuels, particularly coal and fuel oil, are used for residential heating in winter. There is a mineral industrial area at the east of city contains several stone quarries, concrete plants, asphalt plants and lime kiln. The study area is illustrated in Fig. 1. 2.2. Sampling Three sampling systems were used to collect PM10 and PM2.5 samples from the sources. The first is an in-stack cyclone (Model PF 20357/8, Zambelli Inc., Italy) that

collects PM10 or PM2.5 from the stacks. Many of stack samplings were performed using this device. The designed vacuum flow is 14.2 l min1 and this value was achieved by flow controlled pump. The samplings by the device were continued at least 30 min to ensure the adequate PM deposition on the filter. However, in case of high PM concentration in the stack such as OOR burning boiler, the minimum time could not be achieved. This system is not suitable for temperatures >200 °C. So, the sampling of such sources was performed by taking deposits from dust control devices such as cyclone and bag filter, then resuspending the collected material in a chamber. Finally, PM10 and PM2.5 samples were collected in the chamber. Additions to some industrial sources, the samples of top-soils and slag of EAF-Steel production were sampled using the same system. The last one is ambient air sampler (Model PF 20630, Zambelli Inc., Italy) that were used in samplings of traffic emissions and mineral industries (area source) at the ground level. The designed flow rate of this device is 1 m3 h1. The description of characterized sources and sampling method are summarized in Table 1. To characterize the wind-blown dust from the ground, 29 surface soil samples were collected. These samples were taken from points with different characteristics such as urban areas near main roads, suburban areas, plains, mountains, coasts and farms. The disturbed and undisturbed surface soils were collected. Since the possibility of resuspension of PM from the surface soil by wind increases in case of weak vegetation of land, the soil samples were chosen collecting from such areas. Approximately the same

Fig. 1. The sampling area with the major industrial regions.

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687

Table 1 Descriptions of sampled sources and used sampling systems Source name

Sampling tool

Description

Soil

Resuspension chamber Resuspension chamber Resuspension chamber In-stack cyclone Residue analysis Ambient air samplers Resuspension chamber Resuspension chamber In-stack cyclone In-stack cyclone

Undisturbed top-soil samples form 29 areas (urban, suburban, agricultural, coastal and rural)

EAF-Steel from scrap Slag of EAF-Steel Rim production Marine salt Mineral industries Asphalt plant Ceramic industry Wood burning Burning of olive oil residual Coal burning Fuel oil burning Cement kiln Coal mill Cement mill Lead recovery furnace Natural gas burning power plant Coal burning power plant Tobacco processing Traffic emissions Bell metal casting

Resuspension chamber In-stack cyclone In-stack cyclone In-stack cyclone In-stack cyclone Resuspension chamber In-stack cyclone In-stack cyclone In-stack cyclone Ambient air samplers Resuspension chamber

Dust from bag filter of electric arc furnace of steel production from scrap Dust from slag of electric arc furnace of steel production from scrap Samples from stack of paint booth of rim production from aluminum A sample from Izmir Bay, evaporation and analysis of residual salt Samples collected from area source includes stone quarries, lime kiln, asphalt plants, and concrete plants Dust from the cyclone of stack of asphalt plant Dust from bag filter of ceramic production Samples from stack of stove Samples from the olive oil residual burning boiler Dust from cyclone of boiler burning coal (lignite) Samples from the stack of boiler burning fuel oil no. 4 Samples from the stack of cement kiln Samples from the stack of coal mill of a cement plant Samples from the stack of cement mill of a plant Dust from the bag filter of furnace recoveries lead of car batteries Samples from the stack of natural gas burning power plant (1520 MW) located in industrial area contains many electric arc furnaces of steel production Samples from the stack of coal burning power plant (990 MW) equipped with electrostatic precipitator Samples from the stack of tobacco processing unit equipped with bag filter Samples at a junction of a street canyon. Samplings were performed when the traffic dense was maximum Dust from the bag filter of stack of bell metal casting industry

amount of surface soil was collected from at least 20 points in each sampling area. Thus, a mixture of 20 points was obtained for each area. The soil samples were put into high-density polyethylene (HDPE) bottles after passing through plastic sieve (1 mm mesh size). The samples were homogenized manually prior to resuspension and analysis. Since the slag of EAF-Steel is produced in large amount, and is stored as piles, it is exposed to wind. Besides, transferring it by loaders is also available. Thus, deposition of the slag may be a significant source of PM and trace elements in the study area. As a result, a sample was collected and characterized using the resuspension chamber. After homogenization of the samples, they were put into the dust resuspension chamber and filtered air flow was applied. After waiting for a time to ensure the distribution of PM in the dust collection chamber, PF 20630 sampler was operated to collect PM10 and PM2.5 samples. The operation times were depended on the characteristics of collected samples. The samples contained fine PM in less amounts such as some soils, asphalt and ceramic, etc., were operated in longer time. The operation was continued to ensure adequate deposition on the filter.

One seawater sample was taken from Izmir Bay to characterize marine source. Subsequently, the sample was evaporated in a teflon beaker and the evaporation residue was extracted and analyzed just after the weighing. To characterize traffic source, PM10 and PM2.5 samplings were performed at ground level (2 m) concurrently at a street canyon between 17.00 and 19.30 during 5work-day campaign using PF 20630 samplers. The sampling was performed in summer when the wind velocity was low, to avoid contamination of residential heating sources and long range transport. The elemental composition of traffic source was calculated as the average of these five samples. The samples from the area source (mineral industries) were also collected by PF 20630 sampler, at ground level (2 m) when wind was blowing from the north to minimize interferences from other sources, since a forest is located at the north side of this area. The sampling was performed at the south of the area to ensure maximum mixture of PM emitted from several sources of the area. Cellulose acetate (Sartorius AG, Germany) filters were used in all samplings. The filters were initially weighed

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using a microbalance (Mettler-Toledo AG, Switzerland) capable of weighing 2 lg just after keping for 2 h at 105 °C and then an hour in a desiccator. This procedure was also applied to the filters after sampling. 2.3. Chemical analysis The extraction of the filters was carried out by hot acid digestion procedure. Hot acid digestion procedure has been commonly used previously (Cook et al., 1997; Gao et al., 2002; Sastre et al., 2002). The filters were placed into HDPE bottles and 5 ml of acid solution (1:3 HNO3:HCl, Merck Suprapure, Germany) was added. After shaking overnight at room temperature at 250 rpm, 5 ml five times water-diluted acid solution was added, and the digests were heated at nearly 100 °C, at least for 4 h. Then the volume of the extracts was adjusted to final volume by the same diluted acid solution. The elemental analysis of all samples was performed using an inductively coupled plasma-optical emission spectrometer (ICP-OES) (Perkin Elmer Inc., Optima 2100 DV). The concentrations of Al, Ba, Cd, Ca, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Sr, V and Zn were determined. Three aliquots of Urban Particulate Matter (SRM 1648) from NIST (National Institute of Standards and Technology) were extracted and analyzed along with the samples to determine recovery efficiencies of the extraction procedure for the filters. Percent recovery efficiencies were between 70% and 110% except for Al, K and Cr. The average recoveries of these elements were 42%, 52% and 30%, respectively. The relatively low recoveries of Al and Cr were probably due to their presence in silicate matrices that is difficult to extract (Paode et al., 1999). The recovery efficiency of Ca could not be determined since no certified value is available for this element. The blanks of each sampling systems (n = 10) were analyzed. The reported elemental concentrations are the blank corrected values. The sample to blank (S/B) ratios of the traffic data varied between 1.1 (Cd) and 4.2 (K). These are the minimum S/B values of studied sources. The S/B values of other sources are generally over 10 for all elements. 2.4. Calculations The elemental fractions were created calculating the elemental mass of individual samples for each source types and then dividing to the mass of PM. The standard deviations were also calculated for sources that more than one sample were collected. The uncertainty values were calculated using the following equation: " #0:5 n X 2 Uc ¼ C ðU i =X i Þ i¼1

where Uc is the uncertainty of measured elemental mass fractions; C is the measured elemental fractions; Ui is the standard uncertainty value for each component; and Xi is

the measured value of each component. The standard uncertainty values of microbalance, pipette and repeatability of ICP-OES for analyzed elements were used for the uncertainty calculations. The standard uncertainties of calibration curves, recovery efficiencies and calibration standard solution were not used. 3. Source profile results and discussion The elemental fractions (weight percent by mass), standard deviations and uncertainties are given in Table 2. The sample numbers of some industries such as EAF-Steel, lead recovery furnace, asphalt plant and bell metal casting were only 1; because, the PM of these sources were collected from the PM control devices such as bag filters. Thus, the collected PM represented the emissions of long time. The ratio of sum of characterized element to collected PM varied between 0.02 (rim production) and 0.8 (EAF-Steel). The same ratio of the traffic emissions and wood burning were <0.05. The profiles are discussed in detail below. 3.1. Soil Top-soil profiles are dominated by the terrestrial elements such as Al, Ca, Fe, K and M, and sea salt element, Na, for PM10 and PM2.5. Relatively high standard deviations of elemental concentrations particularly Ca, Fe and Al, show that the spatial distribution of soil profiles may be significantly in study area. As soil profiles may change substantially with respect to location, the obtained profile was not compared to other soils investigated around the world. In this study, the anthropogenic elements such as Cd, Cr, Cu, Ni, Pb, V and Zn were generally found in the fine fraction (<2.5 lm). These elements are enriched approximately two times in the fine fraction compared to PM10. Similar results were reported in the literature (Ho et al., 2003; Chow et al., 2004). 3.2. EAF-Steel Zn, Fe, Pb, and Mn are the main elements emitted from the EAF-Steel. The percent contributions of Pb and Zn in this study (8% for Pb and 32% for Zn) are notably high compared to PM profiles from other studies for steel group, such as 0.76% for Pb and 1.2% for Zn (USEPA, 2002). Our data are also greater than the percent contributions calculated in another study in Croatia (Sofilic et al., 2004). It should be noted that Sofilic et al. (2004) reported these values for PM deposits from dust control devices. Orhan (2005) reported elemental profiles for PM of EAF-Steel from scrap in another city of Turkey similar to profiles found in this study. On the other hand, fractions of the other elements in our study are generally lower than those reported for the US (USEPA, 2002). In addition to Pb and Zn, the steel furnaces are one of the major emitters of other trace elements such as Cd, Cr, Cu and Ni. The calculated fractions

Table 2 Source profile chemical composition (weight percent by mass) for PM2.5 and PM10 in Izmir (F is the elemental mass percent of related PM fraction. Xu and SD mean uncertainty and standard deviation, respectively) Size

n

Al

Ba

Ca

Cd

Cr

Cu

Fe

K

Mg

Mn

Na

Ni

Pb

Sr

V

Zn

Soil

PM10

29 F Xu SD 29 F Xu SD

3.97681 0.06426 1.35107 4.61231 0.11738 1.71942

0.02616 0.00042 0.01069 0.03062 0.00079 0.01318

8.85488 0.12673 8.25490 8.79683 0.18617 8.84164

0.00085 0.00005 0.00079 0.00139 0.00009 0.00162

0.00696 0.00036 0.00439 0.01037 0.00061 0.01914

0.00478 0.00025 0.00418 0.00621 0.00035 0.00462

4.33103 0.06925 1.85638 4.74951 0.12470 1.96274

0.96992 0.01570 0.37932 1.23028 0.03277 0.52551

0.92778 0.01451 0.37198 0.92444 0.02381 0.40763

0.13811 0.00216 0.10836 0.14436 0.00340 0.14840

0.24779 0.00416 0.26279 0.27429 0.00783 0.21712

0.01245 0.00065 0.00619 0.01678 0.00100 0.01163

0.07028 0.00365 0.18078 0.10442 0.00772 0.26055

0.01375 0.00021 0.01174 0.01419 0.00032 0.01070

0.00906 0.00047 0.00303 0.01099 0.00064 0.00396

0.03030 0.00051 0.01625 0.06321 0.00191 0.07813

1

F Xu SD F Xu SD

0.90383 0.06426 NA 0.62030 0.01562 NA

0.05283 0.00042 NA 0.05052 0.00127 NA

1.83758 0.12673 NA 0.72940 0.01837 NA

0.12076 0.00005 NA 0.12578 0.00693 NA

0.71589 0.00036 NA 0.22550 0.01242 NA

0.56094 0.00025 NA 0.46200 0.02545 NA

24.70860 0.06925 NA 21.61700 0.54435 NA

3.61828 0.01570 NA 3.71500 0.09355 NA

0.35124 0.01451 NA 0.26810 0.00675 NA

1.62831 0.00216 NA 1.50110 0.03780 NA

3.97200 0.00416 NA 3.98570 0.10037 NA

0.24006 0.00065 NA 0.02014 0.00111 NA

8.44367 0.00365 NA 9.03920 0.49790 NA

0.00319 0.00021 NA 0.00223 0.00006 NA

0.00812 0.00047 NA 0.00683 0.00038 NA

32.89020 0.00051 NA 35.86740 0.90319 NA

F Xu SD F Xu SD

2.58615 0.03178 NA 2.97632 0.03657 NA

0.37016 0.00455 NA 0.37209 0.00457 NA

23.00274 0.28267 NA 24.13800 0.29662 NA

0.02452 0.00030 NA 0.03124 0.00038 NA

0.10040 0.00123 NA 0.09642 0.00118 NA

0.24794 0.00305 NA 0.62086 0.00763 NA

19.48887 0.23949 NA 19.94631 0.24511 NA

1.08629 0.01335 NA 1.30662 0.01606 NA

2.81695 0.03462 NA 3.10232 0.03812 NA

0.55931 0.00687 NA 0.58186 0.00715 NA

3.66276 0.04501 NA 4.37340 0.05374 NA

0.03788 0.00047 NA 0.04903 0.00060 NA

1.87316 0.02302 NA 2.31471 0.02844 NA

0.05366 0.00066 NA 0.05669 0.00070 NA

0.01432 0.00018 NA 0.01628 0.00020 NA

9.05294 0.11125 NA 11.23726 0.13809 NA

F Xu SD F Xu SD

0.78278 0.02348 NA 0.82502 0.02475 NA

0.06185 0.00186 NA 0.14760 0.00443 NA

0.52565 0.01577 NA 0.41522 0.01246 NA

0.00026 0.00001 NA 0.00021 0.00001 NA

0.01381 0.00041 NA 0.03609 0.00108 NA

0.01608 0.00048 NA 0.01521 0.00046 NA

0.53478 0.01604 NA 0.49854 0.01496 NA

0.05958 0.00179 NA 0.04318 0.00130 NA

0.11035 0.00331 NA 0.26213 0.00786 NA

0.00928 0.00028 NA 0.00712 0.00021 NA

0.43333 0.01300 NA 0.06949 0.00208 NA

0.01041 0.00031 NA 0.02454 0.00074 NA

0.04761 0.00143 NA 0.01016 0.00031 NA

0.00304 0.00009 NA 0.00510 0.00015 NA

0.00345 0.00010 NA 0.00285 0.00009 NA

0.19817 0.00595 NA 0.05346 0.00160 NA

PM2.5

EAF-Steel

PM10

PM2.5 1

Slag of EAF-Steel PM10

1

PM2.5 1

Rim production

PM10

2

PM2.5 2

Marine salt

a

1

F 0.00110 0.00005 0.31673 Xu 0.00001 0.00000 0.00318 SD NA NA NA

0.00004 0.00007 0.00000 0.00098 0.00000 0.00000 0.00000 0.00001 NA NA NA NA

1.06398 1.50491 0.00004 22.93119 0.00009 0.00010 0.00468 0.00002 0.00033 0.01070 0.01510 0.00000 0.23000 0.00000 0.00000 0.00005 0.00000 0.00000 NA NA NA NA NA NA NA NA NA

Mineral ind.

PM10

3

F Xu SD F Xu SD

0.78995 0.00905 0.08221 1.44326 0.05056 0.06170

0.00663 0.00007 0.00129 0.01017 0.00032 0.00283

30.50410 0.34664 1.71647 22.91579 0.72715 3.11230

0.00020 0.00001 0.00001 0.00158 0.00010 0.00001

0.00415 0.00021 0.00009 0.00439 0.00026 0.00114

0.00240 0.00012 0.00084 0.00164 0.00009 0.00109

0.42375 0.00486 0.02259 0.71940 0.02470 0.05541

0.13473 0.00155 0.04157 0.23685 0.00803 0.01169

0.18601 0.00211 0.02335 0.22258 0.00694 0.03887

0.01234 0.00014 0.00070 0.01701 0.00052 0.00775

0.18272 0.00201 0.01443 0.26473 0.00753 0.05312

0.00338 0.00017 0.00025 0.01829 0.00104 0.03458

0.00621 0.00031 0.00384 0.02342 0.00139 0.00134

0.01915 0.00022 0.00256 0.01450 0.00045 0.00163

0.00372 0.00019 0.00108 0.00613 0.00036 0.00379

0.01846 0.00021 0.00709 0.03778 0.00112 0.00028

F Xu SD F Xu SD

1.14543 0.01336 NA 2.44723 0.09036 NA

0.00590 0.00007 NA 0.01054 0.00039 NA

36.97907 0.43129 NA 26.70615 0.98613 NA

0.00035 0.00002 NA 0.00302 0.00019 NA

0.00655 0.00033 NA 0.00677 0.00042 NA

0.00024 0.00001 NA 0.00008 0.00000 NA

0.62521 0.00729 NA 1.14323 0.04221 NA

0.21059 0.00246 NA 0.35877 0.01325 NA

0.21074 0.00246 NA 0.23892 0.00882 NA

0.01383 0.00016 NA 0.01642 0.00061 NA

0.04119 0.00048 NA 0.16862 0.00623 NA

0.00493 0.00025 NA 0.01268 0.00078 NA

0.00732 0.00037 NA 0.03429 0.00210 NA

0.02158 0.00025 NA 0.01588 0.00059 NA

0.00367 0.00018 NA 0.00747 0.00046 NA

0.01498 0.00017 NA 0.03078 0.00114 NA

PM2.5 3

Asphalt

PM10

1

PM2.5 1

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Source

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690

Table 2 (continued) Size

Al

Ba

Ca

Cd

Cr

Cu

Fe

K

Mg

Mn

Na

Ni

Pb

Sr

V

Zn

Ceramic

PM10 1 F Xu SD PM2.5 1 F Xu SD

n

4.45166 0.05150 NA 7.23211 0.11987 NA

0.02155 0.00025 NA 0.02850 0.00047 NA

5.79558 0.06705 NA 3.89393 0.06454 NA

0.00082 0.00001 NA 0.00080 0.00001 NA

0.00598 0.00007 NA 0.00409 0.00007 NA

0.00907 0.00011 NA 0.00483 0.00008 NA

0.97104 0.01123 NA 1.30976 0.02171 NA

0.55244 0.00639 NA 0.58745 0.00974 NA

1.85049 0.02140 NA 1.36455 0.02260 NA

0.01471 0.00017 NA 0.01682 0.00028 NA

2.45755 0.02840 NA 0.47396 0.00786 NA

0.01013 0.00012 NA 0.00512 0.00008 NA

0.00619 0.00007 NA 0.00971 0.00016 NA

0.03909 0.00045 NA 0.04644 0.00077 NA

0.00497 0.00006 NA 0.01024 0.00017 NA

0.04809 0.00056 NA 0.04113 0.00068 NA

Wood burning

PM10 3 F Xu SD PM2.5 3 F Xu SD

0.06418 0.00183 0.01439 0.08174 0.00211 0.05325

0.00376 0.00011 0.00144 0.00399 0.00010 0.00171

0.60058 0.01713 0.25266 1.09210 0.02822 0.55130

0.00410 0.00012 0.00177 0.00466 0.00012 0.00218

0.08069 0.00230 0.09159 0.00899 0.00023 0.00205

0.00426 0.00012 0.00125 0.00650 0.00017 0.02357

0.12714 0.00363 0.07432 0.15559 0.00402 0.11569

2.90418 0.08284 0.00000 1.59311 0.04116 0.13168

0.02695 0.00077 0.01674 0.03118 0.00081 0.02159

0.00291 0.00008 0.00000 0.00066 0.00002 0.00000

0.03055 0.00087 0.04300 0.02974 0.00077 0.00000

0.00122 0.00003 0.00000 0.00182 0.00005 0.00011

0.00001 0.00000 0.00000 0.00487 0.00013 0.00667

0.01551 0.00044 0.00625 0.01755 0.00045 0.00784

0.00000 0.00000 0.00000 0.00005 0.00000 0.00000

0.06447 0.00184 0.01300 0.14658 0.00379 0.11747

Burning of OOR

PM10 3 F Xu SD PM2.5 3 F Xu SD

0.69250 0.01894 0.23758 1.46092 0.06668 0.33345

0.01207 0.00033 0.01167 0.00116 0.00005 0.00074

1.11816 0.03058 1.59221 0.46963 0.02143 0.24010

0.00023 0.00001 0.00001 0.00041 0.00003 0.00006

0.02356 0.00132 0.02238 0.02571 0.00172 0.00688

0.02512 0.00141 0.01016 0.02467 0.00165 0.00727

0.41304 0.01130 0.14575 0.29830 0.01361 0.07442

19.65121 0.53745 2.36451 18.25362 0.83311 4.21402

0.20099 0.00550 0.22982 0.03299 0.00151 0.01105

0.00747 0.00020 0.00329 0.00164 0.00007 0.00049

8.63075 0.23605 1.45176 7.09640 0.32388 2.13395

0.02047 0.00115 0.02138 0.00930 0.00062 0.00677

0.02308 0.00129 0.00139 0.01323 0.00089 0.00282

0.00395 0.00011 0.00656 0.00143 0.00007 0.00101

0.00001 0.00000 0.00000 0.00001 0.00000 0.00000

0.48611 0.01329 0.01869 0.26728 0.01220 0.12354

Coal burning

PM10 2 F Xu SD PM2.5 2 F Xu SD

8.73716 0.50001 1.61564 9.35152 0.93289 0.64241

0.10240 0.00507 0.00987 0.11811 0.01062 0.00811

12.67946 1.14637 0.44185 14.28450 2.83065 0.32945

0.00078 0.00006 0.00005 0.00127 0.00022 0.00008

0.10525 0.01620 0.00022 0.22079 0.04968 0.00591

0.12286 0.01890 0.00228 0.10313 0.02299 0.00497

5.19712 0.19249 1.12704 5.65004 0.56632 0.11300

0.93496 0.07294 0.34095 0.63451 0.06215 0.10260

0.74375 0.04081 0.04852 0.77413 0.07326 0.11680

0.04283 0.00351 0.00639 0.07511 0.01265 0.01215

4.51743 0.30339 0.26445 4.10399 0.39062 0.32606

0.07178 0.01040 0.00416 0.16185 0.03581 0.00120

0.06221 0.00814 0.01168 0.04960 0.00903 0.00000

0.08806 0.00271 0.00251 0.09478 0.00603 0.00900

0.24271 0.01315 0.01983 0.27487 0.02305 0.03835

0.22474 0.02720 0.03262 0.27221 0.05278 0.01000

Fuel oil burning

PM10 3 F Xu SD PM2.5 3 F Xu SD

2.32163 0.12669 1.15940 1.79259 0.61653 1.14387

0.01664 0.00068 0.00039 0.02490 0.00208 0.02518

7.24752 0.20319 6.74163 2.53061 0.40682 1.31608

0.00098 0.00006 0.00005 0.00233 0.00101 0.00014

0.15580 0.01171 0.07110 0.04210 0.00356 0.05041

0.02263 0.00183 0.02120 0.00830 0.00192 0.00016

1.19200 0.05842 0.23830 0.72809 0.17385 0.01952

2.40864 0.04620 3.39014 1.83564 0.06746 2.39395

1.38465 0.03600 1.44005 1.59583 0.12673 1.65075

0.02132 0.00084 0.00665 0.03330 0.00081 0.04611

6.56327 0.39077 5.03408 2.06391 0.35945 0.89850

3.18935 0.25648 2.84656 2.61648 0.90669 1.52020

0.02255 0.00176 0.01585 0.01330 0.00130 0.01475

0.02510 0.00061 0.02824 0.01650 0.00096 0.01923

9.49917 0.77029 9.00828 8.54244 3.18890 6.51607

0.49619 0.02919 0.36154 0.60800 0.01370 0.84787

Cement kiln

PM10 3 F Xu SD PM2.5 3 F Xu SD

0.96149 0.10599 0.44860 1.12928 0.16615 0.20357

0.03628 0.00400 0.02104 0.03180 0.00468 0.00765

19.81598 2.18448 7.15543 23.06500 3.39352 4.10008

0.01223 0.00148 0.00439 0.00998 0.00155 0.00239

0.11899 0.01435 0.03043 0.15114 0.02344 0.03973

0.01110 0.00134 0.00754 0.01110 0.00172 0.00761

1.70991 0.18850 0.45114 1.63552 0.24063 0.36061

4.62222 0.50955 1.77675 6.75756 0.99423 1.28471

0.33714 0.03717 0.12186 0.46844 0.06892 0.07999

0.01939 0.00214 0.00691 0.02365 0.00348 0.00501

0.69421 0.07653 0.21694 1.18436 0.17425 0.23616

0.06340 0.00765 0.04169 0.08101 0.01256 0.03254

0.01535 0.00185 0.01096 0.02811 0.00436 0.01111

0.05172 0.00570 0.01961 0.02593 0.00382 0.01930

0.04106 0.00495 0.06131 0.00973 0.00151 0.00486

0.29422 0.03243 0.14578 0.54696 0.08047 0.05996

Coal mill

PM10 3 F Xu SD PM2.5 3 F Xu SD

5.80270 0.85184 4.28978 11.22227 2.48742 3.28480

0.05620 0.00825 0.00511 0.08663 0.01920 0.04240

14.69586 2.15735 2.67988 24.93248 5.52630 7.86573

0.00044 0.00007 0.00014 0.00176 0.00040 0.00166

0.20959 0.03244 0.03269 0.43664 0.09912 0.21591

0.24262 0.03755 0.17489 0.20149 0.04574 0.06572

1.88668 0.27696 1.65618 4.70707 1.04333 2.09616

0.91072 0.13369 1.17173 0.51474 0.11409 0.18022

0.46776 0.06867 0.05361 0.60327 0.13371 0.19984

0.04424 0.00649 0.02446 0.11179 0.02478 0.04357

3.66930 0.53865 4.47040 3.21977 0.71366 2.08461

0.13089 0.02026 0.04892 0.31310 0.07107 0.18865

0.09592 0.01484 0.06711 0.07391 0.01678 0.02612

0.02372 0.00348 0.00148 0.04558 0.01010 0.01246

0.01659 0.00257 0.02273 0.10308 0.02340 0.03029

0.36245 0.05321 0.21278 0.47180 0.10458 0.15542

S. Yatkin, A. Bayram / Chemosphere 71 (2008) 685–696

Source

PM10 3 F Xu SD PM2.5 3 F Xu SD

2.49727 0.07633 0.13618 0.63670 0.07382 0.63670

0.04924 0.00150 0.00456 0.01790 0.00207 0.01790

25.47621 0.77870 1.83665 6.47476 0.75065 6.47476

0.00151 0.00005 0.00042 0.00417 0.00048 0.00417

0.08091 0.00247 0.02164 0.04846 0.00562 0.04846

0.00636 0.00019 0.00116 0.01536 0.00178 0.01536

1.85798 0.05679 0.17042 0.56762 0.06581 0.56762

0.90438 0.02764 0.03358 0.20047 0.02324 0.20047

0.42935 0.01312 0.01644 0.14960 0.01734 0.14960

0.03837 0.00117 0.00233 0.01405 0.00163 0.01405

0.14498 0.00443 0.00000 0.24717 0.02866 0.24717

0.02528 0.00077 0.00607 0.02438 0.00283 0.02438

0.00160 0.00005 0.00000 0.00000 0.00000 0.00000

0.05952 0.00182 0.00753 0.02187 0.00254 0.02187

0.00744 0.00023 0.00046 0.00160 0.00019 0.00160

0.09667 0.00295 0.02989 0.04041 0.00469 0.04041

Lead recovery

PM10 1 F Xu SD PM2.5 1 F Xu SD

0.14533 0.00209 NA 0.26207 0.00506 NA

0.00167 0.00002 NA 0.00018 0.00000 NA

0.04000 0.00057 NA 0.02143 0.00041 NA

0.04219 0.00215 NA 0.03593 0.00189 NA

0.00324 0.00017 NA 0.03625 0.00191 NA

0.15053 0.00768 NA 0.00107 0.00006 NA

0.29009 0.00416 NA 0.34521 0.00666 NA

1.17333 0.01684 NA 0.52093 0.01006 NA

0.00033 0.00000 NA 0.00714 0.00014 NA

0.00013 0.00000 NA 0.00011 0.00000 NA

0.53347 0.00765 NA 0.22193 0.00428 NA

0.00403 0.00021 NA 0.00212 0.00011 NA

75.05653 3.83148 NA 32.65510 1.71952 NA

0.00133 0.00002 NA 0.00143 0.00003 NA

0.00466 0.00024 NA 0.00256 0.00014 NA

0.43742 0.00628 NA 0.19064 0.00368 NA

Aliaga PP

PM10 2 F Xu SD PM2.5 2 F Xu SD

4.78325 1.01454 0.01357 6.81822 1.01554 1.42702

0.08194 0.01720 0.01470 0.05542 0.01740 0.01849

9.71635 1.71394 3.00398 6.90867 1.74938 2.45340

0.00300 0.00023 0.00063 0.00000 0.00023 0.00063

0.21957 0.09024 0.00997 0.21854 0.09368 0.11923

0.25133 0.06362 0.08379 0.20888 0.06643 0.00141

1.62354 1.08231 0.08139 2.87914 1.08410 0.57026

0.31516 0.12240 0.16969 0.42875 0.12587 0.12781

0.96436 0.25390 1.09047 0.81084 0.25605 0.13080

0.04164 0.01306 0.01064 0.03601 0.01369 0.00846

2.04195 0.47843 2.13639 1.76398 0.47935 0.45163

0.18055 0.07974 0.06691 0.19841 0.08221 0.09329

0.09397 0.02176 0.05708 0.07152 0.02344 0.00033

0.04192 0.01491 0.01734 0.04486 0.01614 0.00139

0.01606 0.00733 0.00562 0.02660 0.00743 0.00562

0.46390 0.11616 0.27703 0.39673 0.11742 0.05219

11.17977 0.12207 0.66389 6.64366 0.11659 5.22013

0.04857 0.00053 0.01679 0.06599 0.00116 0.06330

5.01499 0.05476 0.81892 3.13080 0.05494 2.33929

0.00110 0.00006 0.00013 0.00091 0.00005 0.00068

0.01638 0.00082 0.01253 0.02185 0.00114 0.01329

0.00646 0.00032 0.00135 0.00798 0.00042 0.00611

2.04824 0.02237 0.25250 1.15683 0.02030 0.78635

1.04425 0.01140 0.63021 2.95476 0.05185 2.16849

0.53913 0.00589 0.28006 1.23975 0.02176 1.11411

0.01707 0.00019 0.00492 0.01067 0.00019 0.00517

0.72639 0.00793 0.29160 3.96362 0.06956 4.18640

0.01943 0.00098 0.00886 0.01129 0.00059 0.00289

0.01806 0.00091 0.00589 0.01176 0.00061 0.00625

0.02714 0.00030 0.00402 0.03147 0.00055 0.02379

0.03924 0.00197 0.01409 0.02135 0.00111 0.00655

0.05889 0.00064 0.03194 0.07009 0.00123 0.03319

Coal burning PP (Soma PP) PM10 3 F Xu SD PM2.5 2 F Xu SD Tobacco processing

PM10 3 F Xu SD PM2.5 2 F Xu SD

2.68736 0.10749 1.31555 2.91403 0.03570 1.07415

0.01549 0.00062 0.00311 0.01598 0.00020 0.00461

4.18714 0.16749 0.58069 7.03253 0.08616 3.84182

0.00016 0.00001 0.00019 0.00035 0.00002 0.00026

0.01554 0.00062 0.01212 0.01940 0.00098 0.01638

0.01869 0.00075 0.02091 0.02332 0.00118 0.01147

2.57183 0.10287 0.34397 2.52717 0.03096 0.34922

0.70756 0.02830 0.11630 0.65284 0.00800 0.11619

0.88535 0.03541 0.18364 0.90204 0.01105 0.13803

0.04835 0.00193 0.00509 0.05108 0.00063 0.01027

0.23963 0.00959 0.37840 0.20560 0.00252 0.03822

0.01856 0.00074 0.00679 0.01803 0.00091 0.00744

0.00429 0.00017 0.00411 0.00532 0.00027 0.00025

0.00779 0.00031 0.00113 0.00499 0.00006 0.00187

0.00335 0.00013 0.00052 0.00210 0.00011 0.00016

0.01157 0.00046 0.00734 0.07962 0.00098 0.07464

Traffic emissions

PM10 5 F Xu SD PM2.5 5 F Xu SD

0.39639 0.05050 0.08995 0.25843 0.06220 0.07841

0.02127 0.00273 0.00605 0.01076 0.00258 0.00311

2.98239 0.38200 3.09709 1.53740 0.37100 0.44399

0.00048 0.00001 0.00026 0.00048 0.00002 0.00036

0.01717 0.00230 0.00869 0.02483 0.00610 0.01863

0.01861 0.00266 0.00841 0.01350 0.00332 0.00644

0.53918 0.06910 0.12943 0.34291 0.08270 0.07700

0.41359 0.05310 0.08904 0.35284 0.08520 0.07102

0.18198 0.02330 0.07074 0.09823 0.02370 0.03864

0.01492 0.00149 0.00602 0.01879 0.00454 0.01805

0.62897 0.08070 0.31149 0.47438 0.11400 0.10772

0.01090 0.00150 0.00581 0.01271 0.00313 0.00701

0.02644 0.00360 0.00855 0.03073 0.00756 0.01377

0.00733 0.00094 0.00308 0.00513 0.00124 0.00068

0.00434 0.00059 0.00161 0.00380 0.00059 0.00084

0.06949 0.00890 0.02624 0.05704 0.01380 0.03314

Bell metal casting

PM10 1 F Xu SD PM2.5 1 F Xu SD

0.09102 0.00100 NA 0.10393 0.00130 NA

0.00196 0.00002 NA 0.00168 0.00002 NA

0.08010 0.00088 NA 0.04113 0.00051 NA

0.02577 0.00028 NA 0.02781 0.00035 NA

0.00062 0.00001 NA 0.00096 0.00001 NA

1.60630 0.01767 NA 1.26940 0.01586 NA

0.22010 0.00242 NA 0.09081 0.00113 NA

0.03838 0.00042 NA 0.04217 0.00053 NA

0.01715 0.00019 NA 0.01434 0.00018 NA

0.00683 0.00008 NA 0.00463 0.00006 NA

0.00108 0.00001 NA 0.00000 0.00000 NA

0.00024 0.00000 NA 0.00023 0.00000 NA

1.43360 0.01577 NA 1.59496 0.01992 NA

0.00003 0.00000 NA 0.00041 0.00001 NA

0.00008 0.00000 NA 0.00035 0.00000 NA

20.25231 0.22278 NA 28.77639 0.35944 NA

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Cement mill

NA: not available. a Obtained from residual analysis.

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in this study for PM10 and PM2.5 indicate that these elements exist in both fine and coarse (>2.5 lm) fractions. 3.3. Slag The elemental profiles of slag PM differ significantly from the EAF-Steel ones. The Fe content was 20% for PM10 and PM2.5, whereas Zn and Pb were 10% and 2%, respectively. These contents show that the most of Zn and Pb produced by the melting processes are emitted by the stack emissions and lesser amounts remain in the slag. Besides, high terrestrial elements particularly Ca content of the slag (24%) indicates that most of terrestrial elements also remain in the slag of EAF-Steel. Mostly the elemental concentrations in PM2.5 are higher than PM10. 3.4. Rim production The profile of the rim production from aluminum shows that Al is the major element emitted from these sources. The Al content of the paint booth is low (0.8%), which might imply that Al is not significantly emitted during this process. The elemental profile of PM10 and PM2.5 showed that most of the elements exist in the fine fraction of the dust emitted from the paint booths.

PM10, and 1.6% in PM2.5 indicating a slightly higher K in the coarse fraction. Literature reported K percentages between 1% and 22% in different types of biomass (Watson et al., 2001; USEPA, 2002; Chow et al., 2004). The higher end of the range (22%) corresponds to wood burning (USEPA, 2002). 3.9. Burning of OOR The residual of olive oil production has been used as fuel recently in Turkey. The OOR is dried prior to usage. Utilization of the residual in boilers for residential heating and industrial purposes are available in Izmir. The PM of OOR burning emits significant amounts of K (19%) and Na (7%). Similar to the profile of wood burning, the content of K in PM10 (19.7%) is slightly higher than PM2.5 (18.3%) indicating that more K exists in the coarse fraction. Being more in the coarse fraction than the fine fraction is also observed for Na. The K content of PM emitted from OOR burning is near to the profiles reported in the literature for several types of biomass which is between 1% and 22% (Watson et al., 2001; USEPA, 2002; Chow et al., 2004). On the other hand, Na content of OOR burning PM is notably higher than the biomass burning results measured elsewhere (Watson et al., 2001; USEPA, 2002; Chow et al., 2004).

3.5. Marine salt 3.10. Ceramic The marine salt profile was obtained from the sea salt; therefore, fractional separation of PM10 and PM2.5 could not be obtained. The marine salt contains Na (30%) and Mg (1.5%) in significant amounts. 3.6. Mineral industries (area source) The profile of PM from the mineral industrial area is dominated by Ca. It is quite reasonable as there are several earth and mineral industries such as stone quarries, asphalt plant, lime kilns and concrete plants, etc., and the top-soil contains Ca rich material. Percent of Ca content in PM10 and PM2.5 fractions were 30% and 22%, respectively. In conclusion, more Ca exists in the coarse fraction of PM, whereas other elements are found in the fine fraction. 3.7. Asphalt Similar to the profile of mineral industries, the profile of asphalt plant is dominated by Ca; however, the Ca content of the asphalt plant is slightly higher, which are 37% and 27% for PM10 and PM2.5, respectively. Similar to the mineral industries, most of the elements exist in the fine fraction except Ca. 3.8. Wood burning Wood burning PM emissions are one of the major emitters of K. Potassium content was about 2% overall, 2.9% in

The profile of the ceramic industry PM is dominated by the terrestrial elements such as Al, Ca, Mg, Fe and K. However, the abundance of Ca (5%) is lower than soil and the other mineral industries. Profiles for this industry might be strongly dependent upon types of raw materials used in production. The most of the terrestrial elements were in the coarse fraction of PM emitted from the ceramic industries. 3.11. Coal burning Lignite (Soma) is widely used for residential heating in Izmir. The major contributors to the coal burning profiles are the terrestrial elements such as Ca, Al, Fe, Na, K, and Mg. The presence of these elements in the PM2.5 is greater than in PM10. In other words, most of these elements exist in the fine fraction. Comparison with other studies in the world regarding the elemental profiles of PM from coal combustion reveals that the percentages of the terrestrial elements in the PM emissions from burning Soma coals are generally higher. This is with the exception of Ca contents, which are slightly lower in case of burning Soma coal (Watson et al., 2001; USEPA, 2002; Chow et al., 2004). This can be affiliated with the higher Ca content of some of the coals studied in the literature than Soma coals (Chow et al., 2004). The trace elemental composition shows that Soma coal is a major source of Cr, Cu, Ni, Pb and V. The PM emitted from burning of Soma coals contain

S. Yatkin, A. Bayram / Chemosphere 71 (2008) 685–696

higher amounts of trace elements compared to the data reported by Watson and co-workers (2001) and Chow and co-workers (2004). The Cr, Cu, Ni, Pb and V percentages in PM2.5 of Soma coal burning are 0.22%, 0.10%, 0.16%, 0.05% and 0.27%. The Cr, Cu, Ni, Pb and V percentages in PM2.5 from coal combustion reported by Chow et al. (2004) were as 0.026%, 0.09%, 0.02%, 0.0055%, and 0.079%, respectively. The same percentages were reported by Watson et al. (2001) as 0.005%, 0.01%, 0.002%, 0.006% and 0.04%, respectively. The percentages for Soma coal burning are significantly higher than these amounts. Similar to terrestrial elements, most of the trace elements were found in the fine fraction in this source group. 3.12. Fuel oil #4 burning In addition to the terrestrial elements, V and Ni are the major elements emitted from sources that burn fuel oil #4. The fractions of V and Ni are around 9% and 3%, respectively. Since the fractions in PM10 were higher than in PM2.5, we can conclude that V and Ni mainly exist in the coarse fraction. It was reported in the literature (USEPA, 2002) that the contents in the fine fraction were higher than in PM10. It is known that the more complete the combustion, the lower the soot emissions and higher fine particle formation (Baumbach, 1996). It was reported that nearly 80% of PM emitted from fuel oil burning power plants consisted of coarse particles (Baumbach, 1996). On the other hand, it was also reported that particles emitted from a modern fuel oil burning boiler are <1 lm (Baumbach, 1996). However, forming of coarser particles by agglomeration along the exhaust channels was also mentioned for this boiler. Thus, it can be concluded that the efficiency of the burning systems affects significantly the size profile of emitting PM. Most of the terrestrial elements are, also, in the coarse fraction. The fuel oil burning profile highly resembles to the reported values by USEPA (2002). The reported V and Ni percentages, on the other hand, are 4.5% and 2.0% in PM2.5, respectively, corresponding to lower contents than in the fine PM in Izmir. Similarly, the content of the trace elements in the fuel oil burning significantly resembles to the reported composition (USEPA, 2002). 3.13. Cement kiln The PM profile from a coal-fired cement plant is found to be dominated by Ca (20%), K (5%), Fe (1.6%) and Al (1%). It should be noted that this plant was producing Portland cement during the sampling. This plant mostly produces Portland cement. The percentages for these elements in PM2.5 are higher than in PM10, therefore, it should be noted that those exist in the fine fraction. Vega et al. (2001), Ho et al. (2003), and Chow et al. (2004) reported several profiles for cement industry dust emissions where the percentages of terrestrial elements differed significantly, which included Ca. The Ca percent for cement industry around the world varied between 19% and

693

36% of which the profile differed significantly with respect to location. The profiles of trace elements are also variable. Percent contents of Cd, Cr, Cu, Pb and V in this study were all greater than the reported values by Vega et al. (2001), Ho et al. (2003) and Chow et al. (2004). Particularly, Cd content is significantly higher with a percentage about 0.01%. This shows that the cement industry in Izmir is one of the major Cd emitters. Similar to terrestrial elements, most of the trace elements are in the fine fraction. 3.14. Coal mill The coal mill PM profile was obtained from a cement plant which uses different types of lignite containing Soma coals. The profile is dominated by terrestrial elements such as Ca (14–24%), Al (6–11%), Fe (2–5%), and Na (4%). This profile highly resembled to the profile of the coal burning emissions. The elemental concentrations in PM2.5 are significantly higher than in PM10 means most of the elements exist in the fine fraction of the coal mill dust. On the other hand, relatively high SD values may indicate the unstable profile of used coal; and thus, unstable PM profile of coal mill dust. Comparing the elemental concentrations of the coal burning and the coal mill PM indicates high content of the coal mill dust, in another word, the coal. Thus, it can be concluded that significant amount of the elements remains in the slag of the coal burning. 3.15. Cement mill The profile of cement mill dust (Portland cement) is also dominated by Ca like the cement kiln profile. Although the Ca content of PM10 (25%) is near to the percentage of cement kiln, the Ca content in PM2.5 (7%) is significantly lower than the cement kiln. The similar pattern was observed for most of other elements, means that most of the elements are found in the coarse fraction. 3.16. Lead recovery The lead recovery furnaces (secondary furnace for car battery melt-down) are considered as main responsible sources for Pb emissions. The percentages of Pb in PM10 and PM2.5 fractions are 75% and 32%, respectively, which indicate that the most of Pb exist in the coarse fraction. The Pb content (32%) in the fine fraction in our study is lower than the reported value (50%) by USEPA (2002). The lead recovery furnace is also a significant emitter of Cd (0.04%). This value is considerably lower than reported content of 0.7% (USEPA, 2002). The differences in Pb and Cd profiles might be attributed to the difference in the recovered scrap materials between the two countries. 3.17. Aliaga power plant This natural gas burning plant with a power of 1520 megawatts is located at an industrial region (Aliaga) where

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several EAF-Steels and some other industries are located. Flue gas flow rate of the plant is about 10 000 000 m3 h1 with the PM load of 7 kg h1. There are four 95-m-high stacks in the plant. This plant is the largest plant among natural gas burning plants and boilers in the sampling area. The most surprising profile was obtained from this source. The elemental profile is dominated by Ca (7%), Al (5%), Fe (2%), Na (2%), and Mg (0.9%). This profile is most probably due to the PM content of the combustion air, since the power plant is located in the heavily polluted industrial region. The reported Al, Ca, Fe, Na and Mg percents are 0.22, 1.04, 0.09, 2.13 and 0.00, respectively (USEPA, 2002). 3.18. Coal burning power plant (Soma plant) Soma power plant is located approximately 100 km far away to the City of Izmir at the northeast. The power of the plant is 990 MW and the flow of flue gas is about 10 000 000 m3 h1. There are two stacks with heights of 150 m and a stack with height of 250 m. The flue gas is cleaned with electrostatic filters. The PM flow is around 3000 kg h1 when nearly half of the capacity is used. The Soma lignite with low calorific content is used as the fuel. Due to its old technology and low efficiency of the filters, the PM content of the flue gas is extremely high. The elemental percentages show that the profile resembles significantly to Soma coal that is used for the residential heating in Izmir. However, significant differences were obtained for the content of Al and Ca. Al content (11.2%) in PM10 collected from the plant stack is slightly higher than the coal used for residential heating, whereas the Ca content of the former (5.0%) is significantly lower than the latter. Most of the terrestrial elements were found in the coarse fraction. Surprisingly, the trace elemental content of the plant PM is considerably lower than the coal used for residential heating. 3.19. Tobacco The profile of tobacco processing is also dominated by the terrestrial elements. The percentages of Ca, Al, Fe, Mg, and K are 5.0, 2.7, 2.5, 0.9, and 0.6, respectively. Generally, the concentrations in PM2.5 are slightly higher than in PM10, means most of the trace elements are found in the fine fraction of the tobacco processing dusts.

nificantly according to location. Watson et al. (2001), Watson and Chow (2001), and Chow et al. (2004) reported several profiles for traffic emissions, which are significantly different in terms of elemental profile. Watson et al. (2001) found that the content of the terrestrial elements were below 0.01%, whereas Chow et al. (2004) reported values between 0.2% and 1.5%. The reported values (generally >1%) by USEPA (2002) are significantly higher than these values. Thus, it can be concluded that profile of the traffic emissions, particularly road dust, differs significantly with respect to location. However, it should be noted that profile of the traffic emissions is dominated by elemental and organic carbon (EC and OC) (Funasaka et al., 1998; Watson and Chow, 2001; Watson et al., 2001; Chow et al., 2004; Giugliano et al., 2005; He et al., 2006). In this study, the measured contents of Ca, Al, Fe, K, Na, and Mg are 2.0%, 0.3%, 0.4%, 0.3%, 0.4%, and 0.2%, respectively. Since the Pb utilization as fuel additive was banned in 2003 in Turkey, Pb is not a fingerprint element of the traffic emissions anyway. The terrestrial elemental concentrations in PM10 are higher than the PM2.5 ones in our study. So, most of them exist in the coarse fraction. Sodium, Cr, Zn, Mn, K, V, Cd, Ni, and Pb are mainly found in the fine fraction. Since OC and EC were not measured for the traffic emissions, the sum of studied 16 elements is only 5% of the collected PM. In another word, most of PM emitted from the traffic sources could not be characterized in this study. The concurrent traffic measurements (n = 5) clearly showed that the emitted PM was mainly fine. Average PM2.5/PM10 ratio was 81.2 ± 14.9%. Many studies supported the fine character of the traffic emissions (Sturm et al., 2003; Gourioua et al., 2004; Samara and Voutsa, 2005; Fang et al., 2006). 3.21. Bell metal casting The profile of bell metal casting PM contains significant amount of Zn (over 20%), Pb (1.5%), Cu (1.5%) and Cd (0.03%). The elemental concentrations in PM2.5 are slightly higher than in PM10 except Cu, means more elements are found in the fine fraction. This emissions was found as it has the second highest Cd concentrations just after the EAF-Steel PM. Similar to EAF-Steel, also the coarse and the fine fractions have significant amounts of Cd. 4. Summary and conclusion

3.20. Traffic emissions Studies on characterization of the traffic source are generally performed near a main road or in a tunnel at the ground level around the world. Thus, the composite profiles of road dust and exhaust emission are obtained (Watson and Chow, 2001; Watson et al., 2001; Chow et al., 2004). Naturally, the terrestrial element contents differ sig-

The chemical composition of PM10 and PM2.5 samples collected from natural sources, industrial sources, traffic and fuel burning emissions were obtained measuring 16 elements. The characterized PM sources are top-soil, marine salt, cement industry, ceramic industry, asphalt plant, mineral industries (area source includes stone quarries, lime kiln, asphalt plants, and concrete plants), wood burning,

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olive oil residual (OOR) burning, coal (lignite) burning, fuel oil #4 burning, natural gas burning power plant located in a highly polluted industrial area, coal burning power plant, electric arc furnace of steel production from scrap (EAF-Steel), slag of these furnaces, lead recovery furnace from car batteries, bell metal casting, rim production from aluminum, tobacco processing and traffic emissions in Izmir area. Three sampling systems were used: an in-stack cyclone, grab/resuspension chamber and ambient air samples. The elemental profiles of the top-soil, soil related industries such as cement, asphalt, ceramic, etc., and coal burning emissions are dominated by the terrestrial elements particularly Ca. Burning of Soma coals is a significant source of trace elements such as Cr, Cu, Ni, Pb and V. Burning of fuel oil #4 emits V and Ni in significant amounts. As reported by the previous studies, burning of different types of biomass is characterized by high K content in emitted PM. In this study, burning of olive oil residual was characterized and found that the Na content of PM is considerably high (7%) additional to K. A natural gas burning power plant (Aliaga PP) and a coal burning power plant (Soma Plant) with low calorific lignite were also characterized in this study. Since the Aliaga PP is located in highly polluted industrial area, the profile of this source is dominated by the most abundant elements in the atmosphere of the industrial region. The profile Soma plant highly resembles to the profile of coal burning for residential heating and industrial purposes. The EAF-Steel, lead recovery furnaces and bell metal casting industry are the major sources of trace elements in the study area. Especially the EAF-Steel emits significant amount of Zn, Pb and Cd whereas the lead recovery furnaces and bell metal casting industries emits Pb and Cu–Zn, respectively. Acknowledgements This study was supported in part by The Scientific and Technical Research Council of Turkey (TUBITAK) (Project No. 103Y031) and Dokuz Eylul University Research Fund. We also greatly thank to Dr. Mustafa Odabasi for guiding of sampling, analysis and reporting. We are grateful for support of Air Pollution Laboratory staff. References Baumbach, G., 1996. Air Quality Control. Springer-Verlag, Berlin. Chow, J.C., Watson, J.G., Kuhns, H., Etyemezian, V., Lowenthal, D.H., Crow, D., Kohl, S.D., Engelbrecht, J.P., Green, M.C., 2004. Source profile of industrial, mobile, and area sources in the big bend regional aerosol visibility and observational study. Chemosphere 54, 185–208. Cook, J.M., Gardner, M.J., Griffiths, A.H., Jessep, M.A., Ravenscroft, J.E., Yates, R., 1997. The comparability of sample digestion techniques for the determination of metals in sediments. Mar. Pollut. Bull. 34 (8), 637–644. Fang, G.C., Wu, Y.S., Rua, J.Y., Huang, S.H., 2006. Traffic aerosols (18 nm6 particle size 618 lm) source apportionment during the winter period. Atmos. Res. 80, 294–308.

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