Science of the Total Environment xxx (2013) xxx–xxx

STOTEN-15403; No of Pages 6

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Science of the Total Environment

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Investigation of temporal and spatial variations in atmosphericconcentrations of PCDDs and PCDFs in Istanbul

Gulten Gunes ⁎, Arslan Saral, Hakan Celikten, S. Levent Kuzu, Selami Demir, Nihan UygurYildiz Technical University, Department of Environmental Engineering, Esenler, 34220 Istanbul, Turkey

H I G H L I G H T S

• Motor vehicle emissions and other combustions were detected as principal sources of PCDD/F.• Concentration of PCDD/F compounds showed significant temporal variation.• Concentrations of furan congeners were higher than that of dioxin congeners.

⁎ Corresponding author at: Yıldız Technical UniversitDepartment of Environmental Engineering, 34220, Esen212 383 53 68.

E-mail addresses: g.gunes18@gmail.com (G. Gunes), sacelikten@hotmail.com (H. Celikten), skuzu@yildiz.edu.tr (seldemir@yildiz.edu.tr (S. Demir), uygur.n@gmail.com (N

0048-9697/$ – see front matter © 2013 Elsevier B.V. All rihttp://dx.doi.org/10.1016/j.scitotenv.2013.10.094

Please cite this article as: Gunes G, et al, InvIstanbul, Sci Total Environ (2013), http://dx.

a b s t r a c t

a r t i c l e i n f o

Article history:Received 28 July 2013Received in revised form 26 October 2013Accepted 26 October 2013Available online xxxx

Keywords:Polichlorinated dibenzodioxinsPolychlorinated dibenzofuransPersistent organic pollutantsToxic air pollutantsAir quality

In this study, temporal and spatial variations of the atmospheric concentrations of polychlorinated-p-dibenzodioxin (PCDDs) and polychlorinated dibenzofuran (PCDFs) congeners were investigated in Istanbul at threedifferent locations. The highest average concentration (3481 fg/m3) was observed at the sampling locationwhich is characterized by mixed source groups during colder months. The lowest average concentration(749 fg/m3) was observed at sampling station which is characterized by semi-urban characteristics. ∑PCDD/Fconcentration showed seasonal variation in this study. The highest average concentration was determined tobe 4373 fg/m3 in winter while the lowest average concentration was determined to be 498 fg/m3 in summer.

© 2013 Elsevier B.V. All rights reserved.

1. Introductıon

Polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs)are ubiquitous persistent organic pollutants (POPs) (Jones and deVoogt, 1999; UNEP, 2009). They are produced as unwanted byproductsfrom thenatural and antropogenic processes (UNEP, 2002) such as solidwaste incinerators (Olie et al., 1977), metallurgical processes (Buekenset al., 2001; Anderson and Fisher, 2002; Quaßet al., 2004), iron and steelfactories (Anderson and Fisher, 2002; Wang et al., 2003; Aries et al.,2006), automobile emissions (Marklund et al., 1987), steel mills(Tysklind et al., 1989) and chemical production processes (Hutzingeret al., 1985). They can be transported over long distances in the

y, Faculty of Civil Engineering,ler, İstanbul, Turkey. Tel.: +90

ral@yildiz.edu.tr (A. Saral),S.L. Kuzu),. Uygur).

ghts reserved.

estigation of temporal and spdoi.org/10.1016/j.scitotenv.20

atmosphere and stored by wet/dry deposition mechanisms in all envi-ronmental systems such as surface water sources, soil, sediment, biotaurban/rural areas, remote areas and polar regions (Hutzinger, 1985;Jones and de Voogt, 1999; Lohmann and Jones, 1998; Lohmann et al.,1999; Schlabach et al., 1996; Lee and Jones, 1999; Jimenez et al., 2000;Cohen et al., 2002; Corsolini et al., 2002; Hilscherova et al., 2003;Minh et al., 2003). They can bioaccumulate in the food chains (Vander Oost et al., 2003) and cause serious health effects in humansand wildlife (WHO, 1997) due to their resistant structure againstphotolitic, chemical and biological degradation processes. Therefore,ambient air monitoring studies were carried out by several researchersto determine their atmospheric concentrations and worldwide envi-ronmental behaviour. According to these studies, atmospheric con-centrations of PCDD/F compounds fluctuate largely for urban areas(Aristizábal et al., 2011; Li et al., 2008; Menichini et al., 2007; Leeet al., 2007). Several factors such as meteorology, topography, cli-mate, source characteristics, and degradation processes affect PCDD/Fconcentrations in the atmosphere (Alcock and Jones, 1996; Abad et al.,1997; Wevers et al., 1993). In addition, in this study, very fluctuatingconcentrations of PCDDs and PCDFs were observed for different loca-tions of Istanbul.

atial variations in atmospheric concentrations of PCDDs and PCDFs in13.10.094

Fig. 1. Sampling domain and stations.

2 G. Gunes et al. / Science of the Total Environment xxx (2013) xxx–xxx

2. Materials and methods

2.1. Sampling site and stations

Three sampling locations were chosen to determine atmosphericPCDD/F concentrations (Fig. 1). Davutpaşa sampling station is char-acterized by mixed source groups such as industrial, residential andtraffic. Yildiz sampling station is located almost in city center which

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Please cite this article as: Gunes G, et al, Investigation of temporal and spIstanbul, Sci Total Environ (2013), http://dx.doi.org/10.1016/j.scitotenv.20

receives high traffic (motor vehicles and ship) emissions. Fenertepesampling station is located out of the city center and surrounded byforest areas and rural settlements. Although there are no industrialactivities in this area, the medical and hazardous waste incinerationplants are located about 8 km northeast and about 12 km southeastfrom the sampling station, respectively.

Ambient air samples were collected monthly between May 2011 andJanuary 2012 by using high volume samplers (TCR TECORA-Echo, ITALY).Ambient air volumes in the range of 645 to 1900 m3 were collected fromthe each sampling station. Meteorological parameters (temperature,wind velocity/direction, relative humidity, etc.) were measured by wire-less weather stations (Davis Vantage Pro 2 Plus) at each sampling station.

2.2. Analytical procedure

Sampling and analyses were conducted in accordance with thereference method of EPA TO-9A. Before sampling, filters were con-ditioned at 450 °C for 5 h and PUFs were precleaned with acetonein soxhlet extractor for 16 h. Extraction, clean up and fractionationwere applied after sampling to all filter and PUF samples. Glasssample cartridge containing the PUF and quartz filter is extractedseparately with toluene for 20 h by using soxhlet extractor. Thesample is spiked with 13C12-labeled extraction standard solution.After extraction step, toluene extract is concentrated in the rotary vac-uum evaporator, re-dissolved in hexane and pre-cleaned by shakingwith 10 mL of concentrated sulfuric acid at laboratory temperature.Pre-cleaned hexane extract is transferred on the top of anthropogenicmulti-layer silica gel column (see US EPA 1613, Chapter 7.5.4) and

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atial variations in atmospheric concentrations of PCDDs and PCDFs in13.10.094

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eluted with hexane. Extract is concentrated with the modifiedKuderna-Danish concentrator up to 0.5–1 ml. Fractionation is sepa-ration of PCDD/F from other similar structures as a final step of thepreparation procedure. For fractionation 1 g of florisil column andcombination of hexane and dichloromethane for elution of PCDD/Fand PCB fractions was used (Fig. 2).

The final extract containing PCDD/Fs is concentrated up to thedryness under a nitrogen stream and then spiked with injectionstandard. Finally, 2-4 μL are injected to HRGC-HRMS. GC: Trace GCUltra equipped with autosampler Thermo Electron Corp. Tri Plus,column STX-500 (60 m × 0.25 mm, film 0.15 μm) Restek MS:Thermo Electron Corp. DFS operated in MID mode, reference gasPerfluorotributylamine (PFTBA) Resolution R10 ≈ 10 000.

Sampling standard solutions (3 ng 37Cl-2,3,7,8 T4CDD) and extrac-tion standard solutions (0.2 ng 13C12–labeled internal standard) wereused to determine the recovery efficiency of sampling and extractionprocesses. Recovery values were determined in the ranges of 61% to91% and 60% to 118% for 13C12 and 37Cl-2,3,7,8 T4CDD respectively.These values meet the sample recoveries of the EPA Method TO 9A.

3. Results and discussion

3.1. Spatial variations of PCDD/F concentrations

∑17PCDD/F concentration ranged from 982 to 4250 fg/m3 with anaverage value of 2245 fg/m3. Toxicity equivalency of ∑17PCDD/Frange from 52 fg I-TEQ/m3 to 229 fg I-TEQ/m3 with an average valueof 123 fg I-TEQ/m3. Similar results have been reported in previous stud-ies by Lohmann et al. (2000) and Li et al. (2010). Mean concentrationsfor each sampling station were shown in Fig. 3. The highest concentra-tions were found at Davutpasa sampling station. Concentrations rangedfrom 190 to 15331 fg/m3 (mean 4250 fg/m3) and 3 to 616 fg I-TEQ/m3

(mean 229 fg I-TEQ/m3) in this station. This region is affected bymixedsource groups being industrial, residential and traffic sources. The inter-city bus terminal (approximately at 1.5 km NE), the foundry industryarea (approximately at 9 km NW), other industrial activities (metal,metal coating, automotive, glass, iron-steel products, textile, castingetc.) and theuse of fossil fuels for domestic heatingpurposes are consid-ered as the cause of high level of PCDD/Fs. The lowest concentrationswere measured at Fenertepe (semi rural station) sampling stationwhich is located at out of the city center and the values of concentra-tions ranged from 98 to 3012 fg/m3 (mean 982 fg/m3) and from 0.04to 213 fg I-TEQ/m3 (mean 52 fg I-TEQ/m3). The values of the PCDD/Fconcentrations and I-TEQs for Yıldız sampling station ranged from 89to 6255 fg/m3 (mean 1502 fg/m3) and from 0.0 to 383 fg I-TEQ/m3

(mean 87 I-TEQ fg/m3) respectively. This station is surrounded by themain traffic arteries therefore traffic emissions are considered as princi-pal source of the PCDD/F compounds in this area. In addition to, theinter-ship pier is located about 1 km south from this sampling station.

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Please cite this article as: Gunes G, et al, Investigation of temporal and spIstanbul, Sci Total Environ (2013), http://dx.doi.org/10.1016/j.scitotenv.20

3.2. Congener profiles

Congener profiles for each sampling station were shown in Fig. 4. Inthis study, OCDD, 1,2,3,4,6,7,8 HpCDD/F and OCDF were found as themost abundant congeners at all sampling stations. This result is in accor-dance with previous studies which have been reported by Abad et al.(2007), Assuncăo et al. (2005) and Aristizábal et al. (2011). The com-bustion sources such as solid waste incinerators (0.231–626 g TEQ/yrfor municipal waste incinerators and 64.5 ng/kg for hazardous wasteincinerator), motor vehicles (for diesel automobile 685 pg/L and716 pg/L, combustion of fossil fuels 21437 ng/kg for wood stovesand 36-25 ng/kg coal combustors) for domestic and industrial pur-poses are reported to be principal sources of these congeners(USEPA, 1996, 1997, 1998; Hagenmaier et al., 1990; Schwind et al.,1991; Nestrick and Lamparski, 1983; Thub et al., 1995). Interestingly,the concentration of 1,2,3,4,7,8,9-HpCDF was found higher duringDecember sampling period than other sampling periods at allsampling stations. Especially, the highest concentration level forthis congener was observed at Davutpasa sampling station as9471 fg/m3 during December sampling period. Metal recovery pro-cesses (Harnly et al., 1995), secondary aluminum smelters, solidwaste incinerators and industrial/utility coal combustors havebeen reported as the most important emission sources of this con-gener by Cleverly et al. (1997). Domestic heating (domestic wastescontaminated with chemicals) is considered as the other source forthe 1,2,3,4,7,8,9-HpCDF congener in this study, due to the increased1,2,3,4,7,8,9-HpCDF concentrations especially in winter months.1,2,3,4,7,8,9-HpCDF (22%), OCDD (17%), 1,2,3,4,6,7,8-HpCDF (15%),1,2,3,4,6,7,8-HpCDD (9%), and OCDF (8%) were found as the main con-tributors for ∑PCDD/F concentrations at Davutpasa sampling station.OCDD (36%), 1,2,3,4,6,7,8-HpCDD (15%), 1,2,3,4,6,7,8-HpCDD (12%),and OCDF (6%) were found as the principal congeners for Yildiz sam-pling station. The congener profile of Fenertepe sampling station wassimilar to congener patterns at Davutpasa sampling station that OCDD(21%), 1,2,3,4,6,7,8-HpCDF (19%), 1,2,3,4,6,7,8-HpCDD (12%) and OCDF(11%) were the principal congeners (Fig. 3). Although the abundant con-geners are similar to all sampling stations, concentrations of PCDDconge-ners at Yildiz sampling station are higher than that of other samplingstations. This situation confirms that the motor vehicle emissions areprincipal emission sources at Yildiz sampling station. 2,3,4,7,8-PeCDF (41%), 1,2,3,6,7,8,-HxCDF (9%), 1,2,3,4,7,8-HxCDF (9%), and2,3,4,6,7,8-HxCDF (8%) were determined as the main contributorsof the I-TEQ concentration according to the average of all samples.Contribution of 2,3,4,7,8-PeCDF to the total PCDD/F was calculatedas 42%, 41% and 40% for Davutpasa, Yildiz and Fenertepe samplingstations, respectively. 2,3,4,7,8-PeCDFwas found to be themost impor-tant congener at all sampling stations which accounted for 43%,40% and 38% of∑PCDD/F for Davutpasa, Yildiz and Fenertepe sam-pling stations, respectively. We found that the congener profiles ofall samples did not change considerably over time in general.

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4 G. Gunes et al. / Science of the Total Environment xxx (2013) xxx–xxx

The relative contribution of PCDD and PCDF conegeners to∑PCDD/Fconcentration is determined by PCDD to PCDF ratio. This ratio givesinformation about the sources and degradation processes of thesecompounds (Lohmann and Jones, 1998). Themean ratios were calcu-lated as 0.5 (0.2-0.7), 1.5 (0.6-7.0), and 0.5 (0.3-0.9) for Davutpasa,Yildiz and Fenertepe sampling stations, respectively. Similarly, I-TEQ values were calculated as 0.19, 0.15, and 0.13 for Davutpasa,Yildiz and Fenertepe sampling stations, respectively. According tothese results, concentrations of PCDF congeners were higher thanthat of PCDD congeners at Davutpasa and Fenertepe sampling sta-tions while concentrations of PCDD and PCDF congeners are almostequal at Yıldız sampling station. Traffic emissions are principal emis-sions sources at Yıldız sampling station, therefore ratio of PCDD conge-ners is higher than that of other sampling stations.

Concentration of OCDD was found higher than that of OCDF duringsummer months. It has been reported that unleaded gasoline vehiclesand diesel trucks (tailpipe emissions) are the most important sources

Please cite this article as: Gunes G, et al, Investigation of temporal and spIstanbul, Sci Total Environ (2013), http://dx.doi.org/10.1016/j.scitotenv.20

especially for PCDD congeners (Cleverly et al., 1997). Except for motorvehicles, other combustion sources such as industrial combustion pro-cesses (at Davutpasa), residential and commercial heating processesand solid waste incineration processes (at Fenertepe) affected ambientair quality at Davutpasa and Fenertepe sampling stations. The meanratio for three sampling stations was found to be 0.88, thereforePCDD/F congener profile is dominated by PCDF congeners in İstanbulambient air. This ratio agrees with the ratios which were reported byYu et al. (2006), and Li et al. (2008), while disagrees with the ratiowhich was reported by Raun et al. (2005) for Houston ambient air.The congener profiles which are characterized by PCDF congeners arerelated to the urban sources (Oh et al., 2002; Lee et al., 2007). PCDDand PCDF congener concentrations were accounted for 37% and 63% ofthe total 2,3,7,8-substituted congeners respectively. Contribution ofthe I-TEQ values to the ∑PCDD/F was calculated as 20% and 80% forPCDD and PCDF respectively. It has been reported that the concentra-tion of the PCDF congeners ismore than 50% of the total PCDD/F concen-tration (Lohmann and Jones, 1998).

3.3. Temporal variations of the PCDD/F concentrations

Temporal variability of the ambient air concentrations of PCDD/Fs isaffected bymany factors; such as source strengths of PCDD/Fs (combus-tion of fossil fuels for domestic and commercial heating) and/or changesin long range air mass transport over sites of study and meteorologicalconditions (temperature inversion, lowermixing height, solar radiation,UV) (Wallenhorst et al., 1997; Sin et al., 2002; Hippelein et al., 1996;Duarte-Davidson et al., 1997; Lee et al., 1999; Lohmann and Jones,1998; Hiester et al., 1995). Therefore, ambient air PCDD/Fs concentra-tion is higher inwinter than that in summer that this casewas explainedas winter effect in the literature (Hippelein et al., 1996; Duarte-Davidson et al., 1997; Lee et al., 1999; Lohmann et al., 1999). Temporalvariation of the PCDD/Fs concentration was shown in Fig. 5. Thelowest concentrations were observed in September as 156 fg/m3 (3 fgI-TEQ/m3) while the highest concentration was observed in Decemberas 6833 fg/m3 (245 fg I-TEQ/m3) according to the average of all sam-ples. Similar results were reported by several researchers in the litera-ture (Krauthacker et al., 2006; Countinho et al., 2007; Lohmann andJones, 1998). Increasing PCDD/F concentrations during winter monthswere observed especially in a particle phase. Mean particle phase con-centrations for three sampling stations were found to be 279 fg/m3

and 4959 fg/m3 in summer and winter, respectively. Mean gas phaseconcentrations were found to be 148 fg/m3 and 123 fg/m3 in summerand winter seasons, respectively. Therefore, combustion of fossil fuelsfor residential/commercial heating purposes during winter period isconsidered as the most important emission source of PCDD/F com-pounds in Istanbul. Interestingly, the concentrations of PCDD/Fs andtotal suspended particulate (TSP) in January decreased significantly.Observed heavy rainfall/snowfall during this sampling period isconsidered as the cause of decreasing TSP and PCDD/F concentrationin winter. It has been reported that a wet deposition mechanism is animportant removal mechanisms for most suspended organic pollutantsin the atmosphere (Assuncăo et al., 2005) that rainfall is a cause of lowlevels of PCDD/F concentrations in the atmosphere (Chang et al., 2003).Higher deposition fluxes have been reported for winter than that forsummer. Duarte-Davidson et al. (1994), Halsall et al. (1997), andWallenhorst et al. (1997) reported a positive relationship betweentotal deposition flux (wet and dry) and rainfall. Although the lowestmean concentration (982 fg/m3) among three sampling stations wasdetermined at Fenertepe sampling station, the highestmean concentra-tion (508 fg/m3) was determined at this sampling station during thesummer season. Possible reasons for this situation: i) medical andhazardous waste incineration plants which are located about 8 km NEand 12 km SE from this sampling station respectively. The prevailingwind directions were determined as N and NE for July and Augustmonths. ii) biochemical and photolitic reaction products of chlorinated

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5G. Gunes et al. / Science of the Total Environment xxx (2013) xxx–xxx

chemicals such as pentachlorophenol, insecticide, fungicide, herbicide.iii) biological sources due to surrounding forests. Leaf waxes, microbialdegradation and herbal odds have been reported as dioxin/furansources by Rogge et al. (1993).iv) Desorption from the reservoir sources(such as soil, sediment, landfill area etc.) due to the increase in vaporpressure.

4. Conclusion

In this study, the mean concentration of the PCDD/F compoundswere determined as 2245 fg/m3 and 123 I-TEQ fg/m3 for Istanbul ambi-ent air. The highest concentration was determined to be 4250 fg/m3

(190–15297 fg/m3) for residential/industrial sampling station whereasthe lowest concentration was determined to be 982 fg/m3 (98–2093 fg/m3) for semi-rural sampling station. Concentrations offuran congeners were higher than that of dioxin congeners, thereforethe congener profiles of Istanbul ambient air were dominated by PCDFcongeners. OCDD, 1,2,3,4,6,7,8-HpCDF, 1,2,3,4,6,7,8-HpCDD and OCDFwere found to be common congeners for all sampling stations and allsampling periods. In addition, the highest concentration level of1,2,3,4,7,8,9-HpCDF was found only during December sampling periodat Davutpaşa sampling station. It was also found that the concentrationof PCDD/F compounds showed seasonal variation in Istanbul ambientair. Mean concentration for winter months was found to be approxi-mately 12 times higher than that for summer months. Therefore, sea-sonality of PCDD/Fs in the Istanbul atmosphere could be said to beaffected by domestic heating processes and temperature inversion inwinter, or photodegradation and OH− radical reactions in summer. Asa result, combustion processes (combustion of fossil fuels and contam-inated domestic wastes, motor vehicles, metal recovery/smelting pro-cess) are considered to be principal emission sources according to,congener profiles of PCDD/F compounds at Istanbul urban atmosphere.

Acknowledgments

The authors would like to acknowledge the financial support of theScientific and Technological Research Council of Turkey (TUBITAK)under project contract no. 110Y063.

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