- Email: [email protected]
Native and oxygenated polycyclic aromatic hydrocarbons in ambient air particulate matter from the city of Sulaimaniyah in Iraq
Accepted Manuscript Native and oxygenated polycyclic aromatic hydrocarbons in ambient air particulate matter from the city of Sulaimaniyah in Iraq Trifa M. Ahmed, Baram Ahmed, Bakhtyar K. Aziz, Christoffer Bergvall, Roger Westerholm PII:
S1352-2310(15)30158-8
DOI:
10.1016/j.atmosenv.2015.06.020
Reference:
AEA 13898
To appear in:
Atmospheric Environment
Received Date: 4 March 2015 Revised Date:
24 April 2015
Accepted Date: 12 June 2015
Please cite this article as: Ahmed, T.M., Ahmed, B., Aziz, B.K., Bergvall, C., Westerholm, R., Native and oxygenated polycyclic aromatic hydrocarbons in ambient air particulate matter from the city of Sulaimaniyah in Iraq, Atmospheric Environment (2015), doi: 10.1016/j.atmosenv.2015.06.020. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
ACCEPTED MANUSCRIPT 1 2
Native and oxygenated polycyclic aromatic hydrocarbons in ambient air particulate matter from the city of Sulaimaniyah in Iraq
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Trifa M. Ahmeda, Baram Ahmedb, Bakhtyar K. Azizb, Christoffer Bergvalla and Roger Westerholma*
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a
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b
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*Corresponding author: Telephone: +46-(0)8-162440; Fax: +46-(0)8-156391; Email: [email protected]
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Keywords: Ambient air, Particulates, Oxygenated Polycyclic Aromatic Hydrocarbons, Polycyclic Aromatic Hydrocarbons, benzo[a]pyrene, dibenzopyrenes, anthraquinone
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ABSTRACT
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The concentrations of 43 polycyclic aromatic hydrocarbons (PAHs) and 4 oxygenated PAHs
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(OPAHs) are reported for the first time in particulate matter (PM10) sampled in the air of the
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city of Sulaimaniyah in Iraq. The total PAH concentration at the different sampling sites
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varied between 9.3 and 113 ng/m3. The corresponding values of the human carcinogen
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benzo[a]pyrene were between 0.3 and 6.9 ng/m3, with most samples exceeding the EU annual
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target value of 1 ng/m3. The highly carcinogenic dibenzopyrene isomers dibenzo[a,l]pyrene,
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dibenzo[a,e]pyrene, dibenzo[a,i]pyrene and dibenzo[a,h]pyrene constituted 0.1-0.4 % of the
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total PAH concentration. However, when scaling for relative cancer potencies using toxic
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equivalency factors, a benzo[a]pyrene equivalent concentration of dibenzo[a,l]pyrene equal to
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that of benzo[a]pyrene was obtained, indicating that the contribution of dibenzo[a,l]pyrene to
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the carcinogenicity of the PAHs could be similar to that of benzo[a]pyrene. A high correlation
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between the determined concentrations of the dibenzopyrene isomers and benzo[a]pyrene was
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found, which supported the use of benzo[a]pyrene as an indicator for the carcinogenicity of
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PAHs in ambient air.
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The
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cyclopenta[def]phenanthren-4-one, benzanthrone, and 7,12-benz[a]anthraquinone, varied
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Unit of Analytical and Toxicological Chemistry, Department of Environmental Sciences and Analytical Chemistry, Stockholm University SE-10691 Stockholm, Sweden
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School of Science, Department of Chemistry, University of Sulaimaniyah, Iraq, Kurdistan Region, Sulaimaniyah, P.O. Box: 170 Sulaimaniyah, Iraq
total
concentrations
of
the
four
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OPAHs,
9,10-anthraquinone,
4H-
ACCEPTED MANUSCRIPT between 0.6 and 8.1 ng/m3, with 9,10-anthraquinone being the most abundant OPAH in all of
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the samples.
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1. Introduction
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Outdoor air particulate matter (PM) pollution is a problem that negatively affects human
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health. The World Health Organization (WHO) has estimated that, in the year 2012, outdoor
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air PM10 pollution caused a premature death of 3.7 million people worldwide before 60 years
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of age (WHO, 2014).
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Atmospheric air PM is chemically very complex and consists of a large number of different
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compounds, of which the major part is still unknown (Goldstein and Galbally, 2007).
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Inhalation of respirable particulates, i.e., PM10, causes cardiorespiratory mortality (Jonathan et
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al., 2000), whereas lung cancer is attributed to a higher degree to exposure to PM2.5 (Harrison
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et al., 2004). PM is emitted from a variety of different sources such as power plants, forest
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fires, industries, wood combustion, automobile exhausts, and cigarette smoke, among others.
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In urban areas, mobile sources such as cars, trucks, and buses have been reported to contribute
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to more than 50 % of the PM pollution (Ostro, 2004).
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A group of compounds associated with ambient PM are polycyclic aromatic compounds
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(PACs). Polycyclic aromatic hydrocarbons (PAHs), a subgroup of PACs, have been suggested
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to be of importance with regard to adverse health effects from PM inhalation (De Kok et al.,
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2006). PAHs are formed from incomplete combustion of organic materials and could be of
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both natural and anthropogenic origin, the latter comprising industrial activities, residential
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heating and vehicular transport (European Commission, 2001; Boström et al., 2002; Lewtas,
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2007). The most studied PAH, benzo[a]pyrene (B[a]P), is currently the only PAH that has
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been classified as a human carcinogen (Group 1) by the International Agency for Research on
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Cancer (IARC) (IARC, 2010a). The European Union (EU) has set a target value for B[a]P in
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the air to 1 ng/m3 (annual mean in PM10), which has been enforced since December 31, 2012
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ACCEPTED MANUSCRIPT (European Parliament and Council, 2004). The Expert Panel on Air Quality Standards
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(EPAQS) in the United Kingdom has recommended an annual average of 0.25 ng/m3 for
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B[a]P as a guideline for air quality (Coleman et al., 2001), whereas the Swedish target level
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for B[a]P in 2015 is 0.3 ng/m3 (Swedish Government, 2005). Other PAHs are carcinogenic to
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animals and are classified as potential human carcinogens by the IARC (IARC, 2010b). In
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addition, some PAHs have been described as priority pollutants by the US Environmental
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Protection Agency (US EPA, 2008).
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One group of PAHs, which have been shown to be highly potent carcinogens in animal tests,
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are the dibenzopyrene (DBP) isomers: dibenzo[a,l]pyrene (DB[a,l]P), dibenzo[a,e]pyrene
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(DB[a,e]P), dibenzo[a,i]pyrene (DB[a,i]P) and dibenzo[a,h]pyrene (DB[a,h]P) (Mary et al.,
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2001; Pufulete et al., 2004), of which DB[a,l]P has been reported to be the most potent
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carcinogen ever tested in rodents (Luch, 2004). The IARC has classified DB[a,l]P as a
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probable human carcinogen and DB[a,i]P and DB[a,h]P as possible human carcinogens
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(IARC, 2010b). The U.S. Department of Health and Human Services has listed these four
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DBPs as anticipated carcinogens to humans (US DHHS, 2015).
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Another PAC subgroup associated with urban PM is oxygenated PAHs (OPAHs). OPAHs
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contain one or more carbonyl groups and could be more toxic to humans than their
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corresponding parent PAHs. Wang et al. reported that OPAH and nitro-PAH fractions in
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PM2.5 displayed direct-acting mutagenicity in the Ames Salmonella assay with 200 % higher
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mutagenicity than the PAH fraction (Wang et al., 2011). OPAHs have previously been
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identified in different types of PM, i.e., air PM and diesel and gasoline exhaust particles
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(Jakober et al., 2006; 2007). OPAHs are also produced in the atmosphere from PAHs trough
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photo-oxidation reactions (Wang et al., 2011). The suspected importance of OPAHs as a toxic
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component in PM has led to an increasing interest in the analysis of this compound class. In a
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study by Wei and co-workers on the association of anthraquinone (AQ) and 24 PAHs in PM2.5
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ACCEPTED MANUSCRIPT with oxidative stress, the authors found AQ to be strongly associated with increased oxidative
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stress in two security guards exposed on a daily basis to PM at a traffic site (Wei et al., 2010).
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AQ has been classified by IARC as a possible carcinogen to humans (Group 2B) (IARC,
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2012). One of the adverse health effects of these compounds could be related to the partition
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of OPAHs in the fine particle ≤ 2.5 µm size ranges, as shown in a study by Ringuet and
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coworkers (Ringuet et al., 2012a).
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The aim of this present study was to determine the concentrations of PAHs and OPAHs in
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PM10 for the very first time in the city of Sulaimaniyah, Iraq. Special focus was placed on the
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determination of the highly carcinogenic DBPs and OPAHs, which, to our knowledge, have
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never before been determined in Iraq.
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2. Experimental
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2.1. Sampling of urban PM10
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The city of Sulaimaniyah is located on an elevation of 880 m in the region of Kurdistan in
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northeastern Iraq and has a population of approximately 1.5 million inhabitants. The sampling
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of PM was performed during a two-week sampling campaign at the end of 2013/2014 at the
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four most crowded streets in the downtown area of Sulaimaniyah, i.e., Mawlawi, Piramerd,
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Goran, and Kawa streets. Twi Malik Street was also selected as a sampling site and is located
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in a residential area of Sulaimaniyah. The coordinates of the sampling sites, sampling times
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and sampling site abbreviations are shown in Table 1. The PM10 samples were collected using
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an in-house-built sampler consisting of a pump (R O Bin Air, SPX Corp., OH, USA), flow
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meter (G4 Gallus 2000, Denmark) and a filter holder equipped with a glass microfiber filter
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(47 mm EMP 2000, Whatman, England). The sampling train was used in previous air PM10
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sampling campaigns and is described in detail elsewhere (Hopke et al., 1997; Johansson et al.,
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2009). The PM sampling was carried out on the street level at a height of 1.6 m, except for the
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location of Twi Malik Street where the sampling was conducted on the rooftop at a height of 3
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samples collected on the rooftop at Twi Malik Street (T3 and T1 in Table 1). The sampling
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time ranged between 5-6 h at each location, with a flow rate of 34 L/min. The weather
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conditions were mostly sunny, with ambient temperatures ranging between 5-11°C during the
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sampling campaign. However, the weather condition during the sampling of sample G2 was
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heavy rain and that during the collection of sample T3 was windy. After sampling, the filter
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samples were wrapped in aluminum foil prior to shipping by courier to Stockholm University
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for PAH and OPAH analysis. The collected filter samples were stored in a freezer in the
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laboratory prior to the chemical analysis. Furthermore, transport blanks were also subjected to
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PAH and OPAH analysis.
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2.2. Chemicals
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The solvents used in this present study were hexane, toluene, methyl tert-butyl ether (MTBE)
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all of HPLC-grade (Rathburn Chemicals Ltd, UK), ethanol (Kemetyl AB Haninge, Sweden)
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and anhydrous dodecane (> 99 %, Sigma-Aldrich, St. Louis, MO, USA). A complete list of
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PAH and OPAH standards and surrogate internal standards, with supplier information and
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purity used in the present study, are shown in the electronic supporting information, Table S1.
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2.3. Chemical Analysis
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2.3.1. Extraction and clean-up
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The filter samples were extracted using an accelerated solvent extraction system (ASE 200,
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Dionex Corporation, Sunnyvale, CA, USA). Toluene was used as the extraction solvent. A
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commercial mixture of five perdeuterated PAH surrogate internal standards, phenanthrene-
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D10, pyrene-D10, benz[a]anthracene-D12, benzo[a]pyrene-D12, benz[ghi]perylene-D12 in
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toluene and anthraquinone-D8 (Chiron AS, Trondheim, Norway), was added to the sample
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filters prior to extraction. When the extraction was complete, the extracts were evaporated to
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approximately 5 ml under a gentle gas stream of nitrogen while being heated to approximately
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ACCEPTED MANUSCRIPT 60 °C in a water bath (TurboVap® LV evaporator, Zymark, Hopkinton, MA, USA). The
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extracts were transferred to disposable test tubes followed by further evaporation to
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approximately 0.5 ml. The concentrated extracts were added into silica solid-phase extraction
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(SPE) cartridges (100 mg, Isolute, IST, UK) that had been conditioned with 3 mL of hexane
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prior to use. The PAHs and OPAHs were eluted with 2 mL of toluene. A detailed description
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of the extraction procedure and the SPE clean-up method for PAHs and OPAHs can be found
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in detail elsewhere (Ahmed et al., 2014).
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2.3.2 Instrumental analysis
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A
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spectrometry (HPLC-GC/MS) system was used for the separation and detection of the PAHs
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and OPAHs in this present study. The HPLC system consisted of an auto sampler (CMA/200
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microsampler, CMA Microdialysis AB, Sweden), a HPLC pump (Varian Inc, Palo Alto, CA,
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USA) and a normal phase LC column (Nucleosil 100-5NO2 124 × 4.6 mm, 5 µm). The
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GC/MS system consisted of an Agilent 6890N gas chromatograph (Agilent Technologies,
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Palo Alto, CA, USA) with an Agilent 5973N MSD (Agilent Technologies). The set-up and
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operation of the on-line HPLC-GC/MS system for the determination of PAHs and OPAHs is
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described in detail elsewhere (Ahmed et al., 2014; Sadiktsis et al., 2014).
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3. Results and discussion
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3.1. PAHs
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Table 2 shows the concentrations of the 43 PAHs determined in the PM10 samples. In this
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present study, of the total 11 samples, only two samples were sampled during the evening or
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at night-time, i.e., T2 and T3, respectively. The total PAH concentrations ranged between 9.3
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ng/m3 and 90.6 ng/m3. The lowest PAH concentrations were determined during the night-time
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(sample T3). A relatively large variation was found for the sum of the PAH concentration
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between different sampling sites, and the variation was found at the same locations as well.
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ACCEPTED MANUSCRIPT Sample M2 had a larger total PAH concentration in comparison with M1 by a factor of 3; the
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samples were taken at the same location but at different occasions (M2 was taken the day
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after M1). The same variation in the total PAH concentration for locations P, G and K was
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approximately 2. Large day-to-day variations in the PAH concentrations in urban
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environments were previously reported (Albinet et al., 2007). In Sulaimaniyah, electrical
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power generators running on diesel fuel are usually located in each neighborhood as
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additional power supplies when the electricity produced outside the city is turned off. The
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duration of usage of such power generators, as well as variations in the traffic intensity, could
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be the reasons behind the high variations in the PAH concentrations obtained. Calculated as
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an average of all of the samples, the most abundant PAHs were pyrene, fluoranthene,
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phenanthrene, benzo[e]pyrene and B[a]P. Fluoranthene, pyrene and phenathrene were
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reported to be the most abundant PAHs in air PM collected at traffic sites in several studies
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(Wang et al., 2011; Ringuet et al., 2012b). Furthermore, Wang and coworkers (Wang et al.,
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2014) reported that phenanthrene was the most dominant among 16 PAHs in air PM in
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Tianjin, China. However, large changes in the PAH profiles were also obtained with, for
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example, relatively high concentrations of low-molecular-weight PAHs such as phenanthrene,
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anthracene, methylated phenanthrenes and 2-methylanthracene that were obtained in some
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samples (M2, P2 and G1). These results indicate a variation in the contribution of the PAH
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sources. Methylated phenanthrenes have been suggested to originate from unburned fossil
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fuel emissions (Harrison et al., 1996; Youngblood and Blumer, 1975; Poster et al., 2003) and
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have been recommended to be monitored in ambient air due to relatively high air
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concentrations and biological activity (Boström et al., 2002). The mean concentration values
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for B[a]P and the four DBPs for the sample sites M, P, G and K are shown in Table 3
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together with data from the literature for different cities in Europe, Asia and South America.
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The average concentrations of DB[a,l]P, DB[a,e]P, DB[a,i]P, and DB[a,h]P, determined in
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ACCEPTED MANUSCRIPT the present study were much lower than the data reported by Layshock et al. from samples
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collected during winter time in Beijing, China, (Layshock et al., 2010) and were generally
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higher or much higher compared with air PM concentrations reported from Beijing, China
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(summer time) (Layshock et al., 2010), Rome, Italy (Menichini and Merli, 2012); Limeira,
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Brazil (Jarvis et al., 2014) and Stockholm, Sweden (Westerholm et al., 2012). The average
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concentration of DB[a,l]P in Sulaimaniyah was similar to that reported by Slezakova and
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coworkers from one study in Porto, Portugal (Slezakova et al., 2011), whereas the authors
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reported a three-fold higher DB[a,l]P concentration in Porto in another study. The average
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B[a]P concentration determined in the downtown areas of Sulaimaniyah was relatively high
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compared with all of the other cities in Table 3 except for Kabul and winter time sampling in
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Beijing , where the concentrations were more than seven times higher than in the present
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study, Table 3. The concentrations of B[a]P determined in the present study were higher than
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data recently reported in air PM samples collected at two urban sites in Jeddah, Saudi Arabia,
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where average B[a]P levels were 0.35 and 0.27 ng/m3, respectively (Alghamdi et al., 2015).
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However , B[a]P concentrations in this study were similar to previous data reported from air
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PM collected at the Daura Refinery in Bagdad, Iraq, where concentrations in the range of 2.5-
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4.9 ng/m3 were obtained (Shanshal et al., 2014).
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3.2. OPAHs
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The OPAH concentrations determined in Sulaimaniyah PM10 are shown in Table 4. The
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OPAH displaying the highest concentration in all of the samples was AQ, which varied
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between 372 and 4260 pg/m3. The lowest abundant OPAH in all of the samples was 7,12-
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benz[a]anthraquinone (BaAQ) with a concentration in the range of 30-319 pg/m3. The mean
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concentrations of the OPAHs determined in the sample sites M, P, G and K, i.e., the
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downtown areas of Sulaimaniyah, are shown in Table 5. Similar to the PAH concentrations,
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the lowest values were obtained in T3, and high day-to-day variations were obtained. In
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ACCEPTED MANUSCRIPT comparison, the average concentration of AQ determined in the present study was comparable
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with the concentration in Kabul, Afghanistan (Wingfors et al., 2011) and higher than that in
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Santiago, Chile (María, 2006); Augsburg, Germany (Johansson et al., 2009); Paris, France
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(Ringuet et al., 2012a) and Mazar-e Sharif, Afghanistan (Wingfors et al., 2011). The
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corresponding concentrations of the other three OPAHs, Table 5, were lower than the
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concentrations reported from Santiago, Kabul and Augsburg and larger than those reported
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from Paris and Marseilles. Ringut et al. reported that AQ was the most abundant OPAH in air
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PM collected at a traffic site. Albinet et al. found that gasoline was an important source for
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OPAHs, whereas Feilberg et al. stated that the most likely source for benzanthrone (BAQ) in
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Kopenhagen was diesel vehicles (Ringuet et al., 2012a; Albinet et al., 2007; Feilberg et al.,
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2001). The average concentration of AQ was in the range of the most abundant PAH
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determined in this present study. Despite the lack of information on the sources of these
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highly toxic compounds, gasoline and diesel combustion could be possible primary emission
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sources of the OPAHs in the air PM of the Sulaimaniyah downtown area.
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3.3 Carcinogenic risk assessment of the DBPs
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Because of the high toxicity of the DBP isomers and because their concentrations in air were
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only reported in a few studies, we investigated their influence on the assessment of the
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carcinogenic risks relative to B[a]P. There are, in principal, two methods that are applied for
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the carcinogenic risk assessments of PAHs in air, i.e., the surrogate method using B[a]P as a
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marker substance for the entire PAH mixture and the toxic equivalency factor (TEF) approach
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in which B[a]P equivalent concentrations are derived from the multiplication of individual
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PAH concentrations with their carcinogenicity relative to B[a]P (i.e., TEF values) (Pufulete et
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al., 2004; Delgado-Saborit et al., 2011). B[a]P equivalent concentrations were calculated for
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the DBPs using the highest TEFs reported in the literature (Boström et al., 2002), shown in
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Table 6, to prevent any possible underestimation of the relative B[a]P equivalent
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DBPs were clearly for DB[a,l]P, which had a value similar to that of B[a]P. This result was in
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accordance with previous studies, although higher values were reported for DB[a,l]P than for
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B[a]P, as shown in Table 6. The concentrations determined for B[a]P in downtown
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Sulaimanyah for the locations M, P, G and K were in the range of 1.3-6.9 ng/m3, as shown in
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Table 2, which indicated that the calculation of an annual mean concentration would possibly
239
exceed the EU yearly target value of 1 ng/m3 (European Parliament and Council, 2004), the
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Swedish target level for 2015 of 0.3 ng/m3 (Swedish Government, 2005) and the average of
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0.25 ng/m3 for B[a]P in the United Kingdom (Coleman et al., 2001). However, this result
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needs to be confirmed by an additional yearly PM10 measurement. A prerequisite for using
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B[a]P as a marker for the carcinogenicity of the complex mixture of PAHs in air is that the
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relative concentration profiles show high temporal and spatial stability. A high correlation
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between the concentrations of B[a]P and the DBPs was shown in air PM collected throughout
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a year in Rome by Menichini and Merli (Menichini and Merli, 2012). This correlation was
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also investigated in the present study, and the correlation between the B[a]P concentrations
248
and the sum of the four DBP isomers was calculated, shown in Fig S1, resulting in a
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correlation coefficient of R2 = 0.96. This result supported the findings of Menichini and Merli
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of using B[a]P as a marker for the sum of the DBP isomer concentrations. The correlation
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coefficients for the individual DBPs vs. B[a]P were 0.89, 0.96, 0.94 and 0.72 for DB[a,l]P,
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DB[a,e]P, DB[a,i]P and DB[a,h]P, respectively.
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4. Conclusions
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In total, 43 PAHs and 4 OPAHs were detected and quantified at five locations in the city of
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Sulaimaniyah, Iraq for the first time. This study is, to our knowledge, the first to report
256
concentrations of DBPs and OPAHs in air PM10 from Iraq. The average level of the
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carcinogenic PAH B[a]P in Sulaimaniyah PM10 was higher than the legislated EU target value
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by a factor of three. The average level of this compound was even higher than previous
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Sweden and Rome, Italy. A strong linear correlation was found between the B[a]P and DBPs,
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which supports the use of B[a]P as a marker in risk assessments. Among the 4 OPAHs, AQ
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accounted for more than 60 % at each sampling location. OPAHs, especially AQ, were
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considered mutagenic, and they were mostly associated with fine particles, which is why it is
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important to perform additional studies on localizing the source and formation of OPAHs in
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Sulaimaniyah air. The air in Sulaimaniyah is very polluted and most likely negatively affects
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the health of its inhabitants. These results highlight the fact that more investigations need to
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be performed on the formation and sources of the PAC in ambient air and their correlation
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with the local and foreign sources because of their potential toxicity and the lack of data.
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5. Acknowledgement
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Billy Sjövall at SLB-analys, Stockholm, is acknowledged for lending us the PM10 sampling
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equipment, Shaafan M. Hamza from Asia clinical lab is acknowledged for assisting with the
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sampling.
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Ioannis Sadiktsis for his comments on this manuscript. This study was financed by Stockholm
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University and University of Sulaimaniyah.
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6. References
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Ahmed T. M., Bergvall C., Åberg M., Westerholm R., (2014). Determination of oxygenated and native polycyclic aromatic hydrocarbons in urban dust and diesel particulate matter standard reference materials using pressurized liquid extraction and LC-GC/MS. Anal Bioanal Chem. http://download.springer.com/static/pdf/597/art%253A10.1007%252Fs00216-0148304-8.pdf?auth66=1424979073_b2837d358da896e5e3010c1a67631bbd&ext=.pdf
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Albinet A., Leoz-Garziandia E., Budzinski H., Villenave E., (2007). Polycyclic aromatic hydrocarbons (PAHs), nitrated PAHs and oxygenated PAHs in ambient air of the Marseilles area (South of France): concentrations and sources. Sci. Total Environ. 384(1-3): 280-292.
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Algahamdi M., Alam M.S., Yin J., Stark C., Jang E., Harrison R.M., Shamy M., Khoder M.I., Shabbaj I.I., (2015) Receptor modelling study of polycylic aromatic hydrocarbons in Jeddah, Saudi Arabia. Sci. Total Environ. 506-507:401-408.
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Table 1. Sampling sites, abbreviations, date and duration.
Mawlawy street
M1
131226
10:24 Am, 6 h
Mawlawy street
M2
131227
10:08 Am, 6 h
Piramerd street
P1
131228
10:48 Am, 6.25 h
Piramerd street
P2
131229
10:55 Am, 6 h
Goran street
G1
131230
11:05 Am, 6 h
Goran street
G2
131231
11:10 Am, 5.75 h
Twimalik(roof)
T1
140102
05:55 Pm, 4.25 h
Twimalik (roof)
T2
140103
12:08 Am, 5.5 h
Twimalik (roof)
T3
140103
06:40 Pm, 5 h
Kawa street
K1
140104
10:13 Am, 5.5 h
Kawa street
K2
140105
10:10 Am, 5.5 h
Latitude
Longitude
35° 33' 21.51" N
45° 26' 12.55"E
35° 33' 29.94 N
45° 26' 38.53"E
35° 33' 25.75" N
45° 26' 41.86"E
35° 33' 53.68" N
EP AC C
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Start time and Duration
SC
Sampling date
45° 27' 4.807"E
M AN U
Abbreviation
35° 33' 12.9" N
TE D
Sampling site
45° 26' 22.68"E
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Table 2. PAH concentrations (pg/m3) in Sulaimaniyah city. G2 1110 282 785 1050 158 759 776 492 272 206 1040 3320 5240 444 358 228 366 485 456 2860 369 205 463 2432 130 191 212 92.7 2480 1120 2990 2880
T1 1200 220 372 486 87 309 353 246 416 290 541 2760 3500 576 427 266 289 366 422 1700 421 93 564 2770 212 176 223 88 3290 1660 3100 3550
T2 680 105 226 214 13 168 178 113 191 51 279 1550 1870 254 193 104 130 184 167 930 255 56.1 192 1390 50.4 68.7 68.2 36.8 1340 689 1270 901
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G1 4600 618 2810 3520 700 2760 2401 1130 821 595 3350 6070 8540 923 643 676 360 984 1120 4260 1020 430 1200 5520 261 405 471 203 5210 2510 5310 6860
SC
P2 12000 1750 6110 7490 1790 4220 4410 1870 254 471 484 1760 2570 386 275 181 413 467 431 1470 329 96.6 369 1900 222 175 179 81.3 2040 784 2210 2180
M AN U
P1 1490 235 467 595 153 330 374 272 287 128 455 2200 2790 289 266 195 108 323 340 1590 364 100 455 2270 169 197 208 97.0 2380 1010 2535 2910
TE D
M2 21803 3460 6410 7780 2080 3860 5160 4240 387 176 518 2800 3680 430 391 257 429 475 516 2180 497 88.5 645 3030 197 252 267 126 2730 1370 3340 3700
EP
M1 945 108 451 561 101 288 325 146 204 69 561 1470 2050 287 244 165 332 369 359 1620 369 88.9 374 1830 124 183 173 72.3 1760 866 2320 2130
AC C
Compound Phenanthrene Anthracene 3-Methylphenanthrene 2-Methylphenanthrene 2-Methylanthracene 9-Methylphenanthrene 1-Methylphenanthrene 4H-cyclopenta[def)phenanthrene 2-Phenylnaphthalene 3,6-Dimethylphenanthrene 3,9-Dimethylphenanthrene Fluoranthene Pyrene 1-Methylfluoranthene Benz[a]fluorene Benz[b]fluorene 2-Methylpyrene 4-Methylpyrene 1-Methylpyrene Benzo[ghi]fluoranthene Benzo[c]phenanthrene Benzo[b]naphto[1,2-d]thiophene Benz[a]anthracene Chrysene 3-Methylchrysene 2-Methylchrysene 6-Methylchrysene 1-Methylchrysene Benzo[b]fluoranthene Benzo[k]fluoranthene Benzo[e]pyrene Benzo[a]pyrene
T3 671 100 102 126 5.90 77.3 96.2 88.8 128 27.9 114 1030 1130 121 84.9 48.8 60.2 83.6 92.0 523 140 28.6 65.9 738 46.3 32.2 27.8 18.3 764 375 782 295
K1 723 101 208 275 34.9 160 186 138 143 57.5 208 1330 1720 227 191 193 171 206 186 1460 277 68.8 241 1630 86.9 119 114 60.4 1780 750 1940 1330
K2 1120 192 475 585 109 344 401 361 202 123 489 2410 3870 444 356 230 376 501 476 3400 540 170 659 3850 206 242 279 133 4010 1790 4300 3860
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265 73.5 1210 41.6 83.0 1820 25 114 1480 49.9 29.0
800 183 3250 116 215 4200 58 341 3095 119 56.0
2.63 x 104
9.06 x 104
3.20 x 104
6.50 x 104
11.4 x 104
397 78.3 1820 45.5 80.6 3120 20.5 113 2430 40.8 12.8
TE D EP
429 143 2130 81.9 156 2400 36.0 188 1560 61.4 31.0
105 59.5 764 26.5 59.2 802 15.0 216 593 24.5 15.3
31.8 37.0 258 16.3 33.9 480 6.00 46.3 377 17.2 < LOD
165 64.7 1130 33.7 76.9 1830 18.2 94.8 1550 31.6 9.4
483 130 2440 71.1 146 3910 40.6 171 3350 78.5 20.7
3.80 x 104
1.6 4 x104
9.32 x 103
2.13 x 104
4.73 x 104
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336 86.1 1450 46.7 95.8 2080 22.5 140 1710 45.0 21.7
SC
446 96.7 1740 55.0 111 2870 27.0 187.0 2390 47.0 22.9
4.20 x 104
M AN U
266 57.2 1130 35 60.0 1960 30.0 111.0 1630 41.2 31.8
AC C
Perylene Indeno[1,2,3-cd]fluoranthene Indeno[1,2,3-cd]pyrene Dibenz[a,h]anthracene Picene Benzo[ghi]perylene Dibenzo[a,l]pyrene Dibenzo[a,e]pyrene Coronene Dibenzo[a,i]pyrene Dibenzo[a,h]pyrene Sum PAH LOD = limit of detection
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Table 3. Average concentrations (pg/m3) of B[a]P, DB[a,l]P, DB[a,e]P, DB[a,i]P and DB[a,h]P determined in the present study and from literature data .
Italy, Rome
Brazil, Limeira
PM size PM10 PM10 PM1.5 PM1.5 PM2.5
Sub urbanb
2009
October- November
PM2.5
City, street
2010
City, traffic-residential area City, traffic-industrial area
2011
Spring, Autumn, winter Spring
NDR
January - December
2010
March
PM10
B[a]P 2020 953 714 23500 25000
DB[a,l]P 92 23.6 23 2869 NDR
EP AC C
City, trafficc
DB[a,i]P NDR NDR 15 6190 NDR
DB[a,h] P NDR NDR 53 9930 NDR
670
NDR
NDR
NDR
NDR
236
3.9
31
8.6
2.6
PM10
83
1.4
19
4.7
1.5
PM10
650
14
70
20
9
PM10
807
9.07
105
32.0
11.4
159
58
26
2013December-January PM10 3232 31 2014 NDR = no data reported, a= city center, b= 4 km away from city center, c=data from city center during day time
Iraq, Sulaimaniyah
DB[a,e]P NDR NDR 259 29300 NDR
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Season/Month Autumm, Winter Winter Summer Winter October- November
SC
Afganistan, Kabul Afganistan, Mazar e Sharif Sweden, Stockholm
Sub urbana
year 2008 2008 2007 2008 2009
M AN U
Sampling site City,traffic City,traffic City, roof
TE D
Country/City Portugal, Porto Portugal, Porto China, Beijing
Reference (Slezakova et al., 2011) (Slezakova et al., 2010) (Layshock et al., 2010) (Wingfors et al., 2011)
(Westerholm et al., 2012) (Menchini and Merli, 2012 (Jarvis et al., 2014) This study
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Table 4. OPAH concentrations (pg/m3) in Sulaimaniyah city. Sampling sites M1
M2
P1
P2
G1
9,10-Anthraquinone (AQ)
2380
3530
2440
1950
4257
4H-cyclopenta[def]phenanthren-4-one (CPPQ)
647
715
457
505
1170
Benzanthrone (BAQ)
815
840
637
616
2390
7,12-Benz[a]anthraquinone (BaAQ)
117
3.66 x 10
90.0 3
3.16 x 10
319 3
TE D EP
T1
T2
T3
K1
K2
1451
2118
1520
372
1950
2740
388
613
390
93
385
618
645
1180
469
127
692
1360
99.0
296
SC
5.27 x 10
126 3
8.13 x 10
3
2.58 x 10
M AN U
3.96 x 10
182 3
AC C
Sum OPAH
G2
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Compound, (Abbreviation)
3
4.21 x 10
3
94.0
2.47 x 10
30.0 3
6.20 x 10
151 2
3.18 x 10
285 3
5.00 x 103
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Table 5. Literature values of the OPAHs determined in this study in pg/m3. OPAH abbreviations are shown in Table 4. Year
Season/Month
PM
AQ
CPPQ
BAQ
BaAQ
Reference
Chile, Santiago
Urban
2000
Winter
PM10
1580
NDR
NDR
1370
(María del Rosario Sienra , 2006)
Urban
2000
Spring
PM10
560
NDR
NDR
470
Germany, Augsburg
Urban
2003/2004
Autum/ winter
PM2.5
1500
1200
NDR
NDR
(Schnelle-Kreis et al., 2009)
France, Marseilles
Urban
2004
July
PM10
1 398
NDR
219
120
(Albinet et al., 2007)
Afganstan ,Kabul
Urbana
2009
October- November
PM2.5
2500
2800
33000
3100
(Wingfors et al., 2011)
Afganistan, Masa-e Sharif
Urbanb
2009
October- November
PM2.5
460
420
6300
860
France, Paris
Traffic
2010
July
PM10
659.8
NDR
46.6
45.2
RI PT
Sampling site
M AN U
SC
Country/City
(Ringuet et al., 2012a)
AC C
EP
TE D
2013-2014 December-January PM10 2587 610 1000 171 This study Iraq, Sulaimaniyah City, trafficc NDR= no data reported, a= City center, b=4 km far away from city center, c= average concentration of OPAHs from city center during day time
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Limeria 807 907 105 320 114
SC
Rome 650 1400 70 200 90
M AN U
Stockholmb 83 140 19 47 15
TE D
Stockholma 236 390 31 86 26
EP
This work 3232 3008 159 580 260
AC C
Compound TEF 1 B[a]P 100 DB[a,l]P 1 DB[a,e]P 10 DB[a,i]P 10 DB[a,h]P a= 2010, b=2011
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Table 6. Average B[a]P equivalent concentrations [TEF x concentration] for B[a]P, DB[a,l]P, DB[a,e]P, DB[a,i]P and DB[a,h]P in Sulaimaniyah down town compared to values calculated from the literature concentration data presented in Table 3.
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TE D
M AN U
SC
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HIGLIGHTS • The first reported air concentrations of PAHs and oxygenated PAHs in PM10 from Iraq • Mean benzo[a]pyrene concentration exceeded the EU target value • The dibenzopyrene and benzo[a]pyrene concentrations were highly correlated
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Electronic Supplementary Material Native and oxygenated polycyclic aromatic hydrocarbons in ambient air particulate matter from the city of Sulaimaniyah in Iraq
a
Unit of Analytical and Toxicological Chemistry,
RI PT
Trifa M. Ahmed, Baram Ahmed, Bakhtyar K. Aziz, Christoffer Bergvall and Roger Westerholm
Stockholm University SE-10691 Stockholm, Sweden
School of Science, Department of Chemistry,
University of Sulaimaniyah,
M AN U
b
SC
Department of Environmental Sciences and Analytical Chemistry,
Iraq, Kurdistan Region, Sulaimaniyah, P.O. Box: 170 Sulaimaniyah, Iraq *Corresponding author: Telephone: +46-(0)8-162440; Fax: +46-(0)8-156391;
TE D
Email: [email protected]
Table S1 List of PAH, OPAH standards and surrogate internal standards, supplier and purity Name Phenanthrene-D10
Supplier
Purity (%)
Chiron AS, Trondheim, Norwaya), Larodan Fine Chemicals AB,
99.3a), 97.2b)
EP
Sweden
b)
Merck, Germany
98.7
Anthracene
Sigma-Aldrich, St. Louis, MO, USA
99.6
3-Methylphenanthrene
Larodan Fine Chemicals AB, Sweden
99.9
2-Methylphenanthrene
Sigma-Aldrich, St. Louis, MO, USA
93.8
2-Methylanthracene
Koch-Light Laboratories, UK
100
9-Methylphenanthrene
Chiron AS, Trondheim, Norway
100
1-Methylphenanthrene
Larodan Fine Chemicals AB, Sweden
98.8
4H-Cyclopenta[def]phenanthrene
Sigma-Aldrich, St. Louis, MO, USA
99.1
3,6-Dimethylphenanthrene
Larodan Fine Chemicals AB, Sweden
96.1
2-Phenylnaphthalene
EGA-Chemie, Steinheim, Germany
94.2
9-Methylanthracene
Koch-Light Laboratories, UK
97.1
3,9-Dimethylphenanthrene
Chiron AS, Trondheim, Norway
99.7
Fluoranthene
Sigma-Aldrich, St. Louis, MO, USA
97.2
AC C
Phenanthrene
1
ACCEPTED MANUSCRIPT Chiron AS, Trondheim, Norwaya), Larodan Fine Chemicals AB,
Pyrene-D10
Sweden
99.8a), 95.7b)
b)
Janssen Chimica, Belgium
97.6
1-Methylfluoranthene
Chiron AS, Trondheim, Norway
99.7
Benzo[a]fluorene
Chiron AS, Trondheim, Norway
98.8
Benzo[b]fluorene
Sigma-Aldrich, St. Louis, MO, USA
99.1
2-Methylpyrene
Chiron AS, Trondheim, Norway
98.3
4-Methylpyrene
Chiron AS, Trondheim, Norway
1-Methylpyrene
Larodan Fine Chemicals AB, Sweden
Benzo[c]phenanthrene
Chiron AS, Trondheim, Norway
Benzo[ghi]fluoranthene
Larodan Fine Chemicals AB, Sweden
Benzo[b]naphto[1,2-d]thiophene
Chiron AS, Trondheim, Norway
99.6
Benz[a]anthracene-D12
Chiron AS, Trondheim, Norway
98.6
Benz[a]anthracene
Fluka AG, Switzerland
98.4
Chrysene
Sigma-Aldrich, St. Louis, MO, USA
96.4
3-Methylchrysene
Chiron AS, Trondheim, Norway
99.1
2-Methylchrysene
Chiron AS, Trondheim, Norway
99.7
6-Methylchrysene
Chiron AS, Trondheim, Norway
100
1-Methylchrysene
Chiron AS, Trondheim, Norway
99.3
Benzo[k]fluoranthene Benzo[e]pyrene
SC
M AN U
EP
Benzo[a]pyrene-D12
TE D
Benzo[b]fluoranthene
RI PT
Pyrene
99.6
99.1
99.5
99.5
Chem Service, West Chester, PA, USA
100
Chem Service, West Chester, PA, USA
98.3
Sigma-Aldrich, St. Louis, MO, USA
99.7
Chiron AS, Trondheim, Norwaya), Larodan Fine Chemicals AB,
98.7a), 98.1b)
Sweden
b)
Sigma-Aldrich, St. Louis, MO, USA
97.6
Perylene
Sigma-Aldrich, St. Louis, MO, USA
99.5
Indeno[1,2,3-cd]fluoranthene
Radiant Dyes, Wermelskirchen, Germany
98.4
Indeno[1,2,3-cd]pyrene
AccuStandard Inc., New Haven, CT, USA
99.8
Dibenz[a,h]anthracene
Fluka AG, Switzerland
99.4
Picene
Larodan Fine Chemicals AB, Sweden
96.1
Benzo[ghi]perylene-D12
Chiron AS, Trondheim, Norway
99.6
Benzo[ghi]perylene
Janssen Chimica, Belgium
98.8
Dibenzo[a,l]pyrene
AccuStandard Inc., New Haven, CT, USA
96
Dibenzo[a,e]pyrene
LGC Promochem, Sweden
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Coronene-D12
Chiron AS, Trondheim, Norway
98.9
Coronen
Radiant Dyes. Wermelskirchen, Germany
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LGC Promochem, Sweden
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Dibenzo[a,i]pyrene
Sigma-Aldrich, St. Louis, MO, USA
96.4
Dibenzo[a,h]pyrene
Koch-Light Laboratories, UK
100
Anthraquinone -D8
Chiron AS (Trondheim, Norway)
99.4
9,10-Anthraquinone
Chiron AS (Trondheim, Norway)
99.5
Cyclopenta[def]phenanthren-4-one Chiron AS (Trondheim, Norway) Chiron AS (Trondheim, Norway)
7,12 Benz[a]anthraquinone
Chiron AS (Trondheim, Norway)
99
98.5
97.5
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Fig S1. Correlation between concentration of B[a]P and total concentration of DBP isomers in PM10.
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S1352-2310(15)30158-8
DOI:
10.1016/j.atmosenv.2015.06.020
Reference:
AEA 13898
To appear in:
Atmospheric Environment
Received Date: 4 March 2015 Revised Date:
24 April 2015
Accepted Date: 12 June 2015
Please cite this article as: Ahmed, T.M., Ahmed, B., Aziz, B.K., Bergvall, C., Westerholm, R., Native and oxygenated polycyclic aromatic hydrocarbons in ambient air particulate matter from the city of Sulaimaniyah in Iraq, Atmospheric Environment (2015), doi: 10.1016/j.atmosenv.2015.06.020. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
ACCEPTED MANUSCRIPT 1 2
Native and oxygenated polycyclic aromatic hydrocarbons in ambient air particulate matter from the city of Sulaimaniyah in Iraq
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Trifa M. Ahmeda, Baram Ahmedb, Bakhtyar K. Azizb, Christoffer Bergvalla and Roger Westerholma*
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a
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b
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*Corresponding author: Telephone: +46-(0)8-162440; Fax: +46-(0)8-156391; Email: [email protected]
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Keywords: Ambient air, Particulates, Oxygenated Polycyclic Aromatic Hydrocarbons, Polycyclic Aromatic Hydrocarbons, benzo[a]pyrene, dibenzopyrenes, anthraquinone
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ABSTRACT
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The concentrations of 43 polycyclic aromatic hydrocarbons (PAHs) and 4 oxygenated PAHs
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(OPAHs) are reported for the first time in particulate matter (PM10) sampled in the air of the
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city of Sulaimaniyah in Iraq. The total PAH concentration at the different sampling sites
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varied between 9.3 and 113 ng/m3. The corresponding values of the human carcinogen
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benzo[a]pyrene were between 0.3 and 6.9 ng/m3, with most samples exceeding the EU annual
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target value of 1 ng/m3. The highly carcinogenic dibenzopyrene isomers dibenzo[a,l]pyrene,
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dibenzo[a,e]pyrene, dibenzo[a,i]pyrene and dibenzo[a,h]pyrene constituted 0.1-0.4 % of the
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total PAH concentration. However, when scaling for relative cancer potencies using toxic
25
equivalency factors, a benzo[a]pyrene equivalent concentration of dibenzo[a,l]pyrene equal to
26
that of benzo[a]pyrene was obtained, indicating that the contribution of dibenzo[a,l]pyrene to
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the carcinogenicity of the PAHs could be similar to that of benzo[a]pyrene. A high correlation
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between the determined concentrations of the dibenzopyrene isomers and benzo[a]pyrene was
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found, which supported the use of benzo[a]pyrene as an indicator for the carcinogenicity of
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PAHs in ambient air.
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The
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cyclopenta[def]phenanthren-4-one, benzanthrone, and 7,12-benz[a]anthraquinone, varied
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Unit of Analytical and Toxicological Chemistry, Department of Environmental Sciences and Analytical Chemistry, Stockholm University SE-10691 Stockholm, Sweden
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School of Science, Department of Chemistry, University of Sulaimaniyah, Iraq, Kurdistan Region, Sulaimaniyah, P.O. Box: 170 Sulaimaniyah, Iraq
total
concentrations
of
the
four
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OPAHs,
9,10-anthraquinone,
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the samples.
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1. Introduction
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Outdoor air particulate matter (PM) pollution is a problem that negatively affects human
37
health. The World Health Organization (WHO) has estimated that, in the year 2012, outdoor
38
air PM10 pollution caused a premature death of 3.7 million people worldwide before 60 years
39
of age (WHO, 2014).
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Atmospheric air PM is chemically very complex and consists of a large number of different
41
compounds, of which the major part is still unknown (Goldstein and Galbally, 2007).
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Inhalation of respirable particulates, i.e., PM10, causes cardiorespiratory mortality (Jonathan et
43
al., 2000), whereas lung cancer is attributed to a higher degree to exposure to PM2.5 (Harrison
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et al., 2004). PM is emitted from a variety of different sources such as power plants, forest
45
fires, industries, wood combustion, automobile exhausts, and cigarette smoke, among others.
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In urban areas, mobile sources such as cars, trucks, and buses have been reported to contribute
47
to more than 50 % of the PM pollution (Ostro, 2004).
48
A group of compounds associated with ambient PM are polycyclic aromatic compounds
49
(PACs). Polycyclic aromatic hydrocarbons (PAHs), a subgroup of PACs, have been suggested
50
to be of importance with regard to adverse health effects from PM inhalation (De Kok et al.,
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2006). PAHs are formed from incomplete combustion of organic materials and could be of
52
both natural and anthropogenic origin, the latter comprising industrial activities, residential
53
heating and vehicular transport (European Commission, 2001; Boström et al., 2002; Lewtas,
54
2007). The most studied PAH, benzo[a]pyrene (B[a]P), is currently the only PAH that has
55
been classified as a human carcinogen (Group 1) by the International Agency for Research on
56
Cancer (IARC) (IARC, 2010a). The European Union (EU) has set a target value for B[a]P in
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the air to 1 ng/m3 (annual mean in PM10), which has been enforced since December 31, 2012
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ACCEPTED MANUSCRIPT (European Parliament and Council, 2004). The Expert Panel on Air Quality Standards
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(EPAQS) in the United Kingdom has recommended an annual average of 0.25 ng/m3 for
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B[a]P as a guideline for air quality (Coleman et al., 2001), whereas the Swedish target level
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for B[a]P in 2015 is 0.3 ng/m3 (Swedish Government, 2005). Other PAHs are carcinogenic to
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animals and are classified as potential human carcinogens by the IARC (IARC, 2010b). In
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addition, some PAHs have been described as priority pollutants by the US Environmental
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Protection Agency (US EPA, 2008).
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One group of PAHs, which have been shown to be highly potent carcinogens in animal tests,
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are the dibenzopyrene (DBP) isomers: dibenzo[a,l]pyrene (DB[a,l]P), dibenzo[a,e]pyrene
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(DB[a,e]P), dibenzo[a,i]pyrene (DB[a,i]P) and dibenzo[a,h]pyrene (DB[a,h]P) (Mary et al.,
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2001; Pufulete et al., 2004), of which DB[a,l]P has been reported to be the most potent
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carcinogen ever tested in rodents (Luch, 2004). The IARC has classified DB[a,l]P as a
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probable human carcinogen and DB[a,i]P and DB[a,h]P as possible human carcinogens
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(IARC, 2010b). The U.S. Department of Health and Human Services has listed these four
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DBPs as anticipated carcinogens to humans (US DHHS, 2015).
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Another PAC subgroup associated with urban PM is oxygenated PAHs (OPAHs). OPAHs
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contain one or more carbonyl groups and could be more toxic to humans than their
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corresponding parent PAHs. Wang et al. reported that OPAH and nitro-PAH fractions in
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PM2.5 displayed direct-acting mutagenicity in the Ames Salmonella assay with 200 % higher
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mutagenicity than the PAH fraction (Wang et al., 2011). OPAHs have previously been
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identified in different types of PM, i.e., air PM and diesel and gasoline exhaust particles
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(Jakober et al., 2006; 2007). OPAHs are also produced in the atmosphere from PAHs trough
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photo-oxidation reactions (Wang et al., 2011). The suspected importance of OPAHs as a toxic
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component in PM has led to an increasing interest in the analysis of this compound class. In a
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study by Wei and co-workers on the association of anthraquinone (AQ) and 24 PAHs in PM2.5
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stress in two security guards exposed on a daily basis to PM at a traffic site (Wei et al., 2010).
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AQ has been classified by IARC as a possible carcinogen to humans (Group 2B) (IARC,
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2012). One of the adverse health effects of these compounds could be related to the partition
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of OPAHs in the fine particle ≤ 2.5 µm size ranges, as shown in a study by Ringuet and
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coworkers (Ringuet et al., 2012a).
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The aim of this present study was to determine the concentrations of PAHs and OPAHs in
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PM10 for the very first time in the city of Sulaimaniyah, Iraq. Special focus was placed on the
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determination of the highly carcinogenic DBPs and OPAHs, which, to our knowledge, have
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never before been determined in Iraq.
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2. Experimental
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2.1. Sampling of urban PM10
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The city of Sulaimaniyah is located on an elevation of 880 m in the region of Kurdistan in
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northeastern Iraq and has a population of approximately 1.5 million inhabitants. The sampling
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of PM was performed during a two-week sampling campaign at the end of 2013/2014 at the
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four most crowded streets in the downtown area of Sulaimaniyah, i.e., Mawlawi, Piramerd,
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Goran, and Kawa streets. Twi Malik Street was also selected as a sampling site and is located
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in a residential area of Sulaimaniyah. The coordinates of the sampling sites, sampling times
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and sampling site abbreviations are shown in Table 1. The PM10 samples were collected using
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an in-house-built sampler consisting of a pump (R O Bin Air, SPX Corp., OH, USA), flow
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meter (G4 Gallus 2000, Denmark) and a filter holder equipped with a glass microfiber filter
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(47 mm EMP 2000, Whatman, England). The sampling train was used in previous air PM10
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sampling campaigns and is described in detail elsewhere (Hopke et al., 1997; Johansson et al.,
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2009). The PM sampling was carried out on the street level at a height of 1.6 m, except for the
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location of Twi Malik Street where the sampling was conducted on the rooftop at a height of 3
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samples collected on the rooftop at Twi Malik Street (T3 and T1 in Table 1). The sampling
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time ranged between 5-6 h at each location, with a flow rate of 34 L/min. The weather
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conditions were mostly sunny, with ambient temperatures ranging between 5-11°C during the
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sampling campaign. However, the weather condition during the sampling of sample G2 was
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heavy rain and that during the collection of sample T3 was windy. After sampling, the filter
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samples were wrapped in aluminum foil prior to shipping by courier to Stockholm University
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for PAH and OPAH analysis. The collected filter samples were stored in a freezer in the
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laboratory prior to the chemical analysis. Furthermore, transport blanks were also subjected to
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PAH and OPAH analysis.
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2.2. Chemicals
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The solvents used in this present study were hexane, toluene, methyl tert-butyl ether (MTBE)
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all of HPLC-grade (Rathburn Chemicals Ltd, UK), ethanol (Kemetyl AB Haninge, Sweden)
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and anhydrous dodecane (> 99 %, Sigma-Aldrich, St. Louis, MO, USA). A complete list of
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PAH and OPAH standards and surrogate internal standards, with supplier information and
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purity used in the present study, are shown in the electronic supporting information, Table S1.
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2.3. Chemical Analysis
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2.3.1. Extraction and clean-up
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The filter samples were extracted using an accelerated solvent extraction system (ASE 200,
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Dionex Corporation, Sunnyvale, CA, USA). Toluene was used as the extraction solvent. A
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commercial mixture of five perdeuterated PAH surrogate internal standards, phenanthrene-
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D10, pyrene-D10, benz[a]anthracene-D12, benzo[a]pyrene-D12, benz[ghi]perylene-D12 in
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toluene and anthraquinone-D8 (Chiron AS, Trondheim, Norway), was added to the sample
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filters prior to extraction. When the extraction was complete, the extracts were evaporated to
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approximately 5 ml under a gentle gas stream of nitrogen while being heated to approximately
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extracts were transferred to disposable test tubes followed by further evaporation to
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approximately 0.5 ml. The concentrated extracts were added into silica solid-phase extraction
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(SPE) cartridges (100 mg, Isolute, IST, UK) that had been conditioned with 3 mL of hexane
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prior to use. The PAHs and OPAHs were eluted with 2 mL of toluene. A detailed description
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of the extraction procedure and the SPE clean-up method for PAHs and OPAHs can be found
139
in detail elsewhere (Ahmed et al., 2014).
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2.3.2 Instrumental analysis
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A
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spectrometry (HPLC-GC/MS) system was used for the separation and detection of the PAHs
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and OPAHs in this present study. The HPLC system consisted of an auto sampler (CMA/200
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microsampler, CMA Microdialysis AB, Sweden), a HPLC pump (Varian Inc, Palo Alto, CA,
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USA) and a normal phase LC column (Nucleosil 100-5NO2 124 × 4.6 mm, 5 µm). The
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GC/MS system consisted of an Agilent 6890N gas chromatograph (Agilent Technologies,
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Palo Alto, CA, USA) with an Agilent 5973N MSD (Agilent Technologies). The set-up and
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operation of the on-line HPLC-GC/MS system for the determination of PAHs and OPAHs is
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described in detail elsewhere (Ahmed et al., 2014; Sadiktsis et al., 2014).
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3. Results and discussion
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3.1. PAHs
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Table 2 shows the concentrations of the 43 PAHs determined in the PM10 samples. In this
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present study, of the total 11 samples, only two samples were sampled during the evening or
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at night-time, i.e., T2 and T3, respectively. The total PAH concentrations ranged between 9.3
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ng/m3 and 90.6 ng/m3. The lowest PAH concentrations were determined during the night-time
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(sample T3). A relatively large variation was found for the sum of the PAH concentration
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between different sampling sites, and the variation was found at the same locations as well.
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samples were taken at the same location but at different occasions (M2 was taken the day
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after M1). The same variation in the total PAH concentration for locations P, G and K was
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approximately 2. Large day-to-day variations in the PAH concentrations in urban
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environments were previously reported (Albinet et al., 2007). In Sulaimaniyah, electrical
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power generators running on diesel fuel are usually located in each neighborhood as
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additional power supplies when the electricity produced outside the city is turned off. The
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duration of usage of such power generators, as well as variations in the traffic intensity, could
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be the reasons behind the high variations in the PAH concentrations obtained. Calculated as
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an average of all of the samples, the most abundant PAHs were pyrene, fluoranthene,
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phenanthrene, benzo[e]pyrene and B[a]P. Fluoranthene, pyrene and phenathrene were
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reported to be the most abundant PAHs in air PM collected at traffic sites in several studies
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(Wang et al., 2011; Ringuet et al., 2012b). Furthermore, Wang and coworkers (Wang et al.,
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2014) reported that phenanthrene was the most dominant among 16 PAHs in air PM in
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Tianjin, China. However, large changes in the PAH profiles were also obtained with, for
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example, relatively high concentrations of low-molecular-weight PAHs such as phenanthrene,
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anthracene, methylated phenanthrenes and 2-methylanthracene that were obtained in some
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samples (M2, P2 and G1). These results indicate a variation in the contribution of the PAH
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sources. Methylated phenanthrenes have been suggested to originate from unburned fossil
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fuel emissions (Harrison et al., 1996; Youngblood and Blumer, 1975; Poster et al., 2003) and
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have been recommended to be monitored in ambient air due to relatively high air
179
concentrations and biological activity (Boström et al., 2002). The mean concentration values
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for B[a]P and the four DBPs for the sample sites M, P, G and K are shown in Table 3
181
together with data from the literature for different cities in Europe, Asia and South America.
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The average concentrations of DB[a,l]P, DB[a,e]P, DB[a,i]P, and DB[a,h]P, determined in
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collected during winter time in Beijing, China, (Layshock et al., 2010) and were generally
185
higher or much higher compared with air PM concentrations reported from Beijing, China
186
(summer time) (Layshock et al., 2010), Rome, Italy (Menichini and Merli, 2012); Limeira,
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Brazil (Jarvis et al., 2014) and Stockholm, Sweden (Westerholm et al., 2012). The average
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concentration of DB[a,l]P in Sulaimaniyah was similar to that reported by Slezakova and
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coworkers from one study in Porto, Portugal (Slezakova et al., 2011), whereas the authors
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reported a three-fold higher DB[a,l]P concentration in Porto in another study. The average
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B[a]P concentration determined in the downtown areas of Sulaimaniyah was relatively high
192
compared with all of the other cities in Table 3 except for Kabul and winter time sampling in
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Beijing , where the concentrations were more than seven times higher than in the present
194
study, Table 3. The concentrations of B[a]P determined in the present study were higher than
195
data recently reported in air PM samples collected at two urban sites in Jeddah, Saudi Arabia,
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where average B[a]P levels were 0.35 and 0.27 ng/m3, respectively (Alghamdi et al., 2015).
197
However , B[a]P concentrations in this study were similar to previous data reported from air
198
PM collected at the Daura Refinery in Bagdad, Iraq, where concentrations in the range of 2.5-
199
4.9 ng/m3 were obtained (Shanshal et al., 2014).
200
3.2. OPAHs
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The OPAH concentrations determined in Sulaimaniyah PM10 are shown in Table 4. The
202
OPAH displaying the highest concentration in all of the samples was AQ, which varied
203
between 372 and 4260 pg/m3. The lowest abundant OPAH in all of the samples was 7,12-
204
benz[a]anthraquinone (BaAQ) with a concentration in the range of 30-319 pg/m3. The mean
205
concentrations of the OPAHs determined in the sample sites M, P, G and K, i.e., the
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downtown areas of Sulaimaniyah, are shown in Table 5. Similar to the PAH concentrations,
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the lowest values were obtained in T3, and high day-to-day variations were obtained. In
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with the concentration in Kabul, Afghanistan (Wingfors et al., 2011) and higher than that in
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Santiago, Chile (María, 2006); Augsburg, Germany (Johansson et al., 2009); Paris, France
211
(Ringuet et al., 2012a) and Mazar-e Sharif, Afghanistan (Wingfors et al., 2011). The
212
corresponding concentrations of the other three OPAHs, Table 5, were lower than the
213
concentrations reported from Santiago, Kabul and Augsburg and larger than those reported
214
from Paris and Marseilles. Ringut et al. reported that AQ was the most abundant OPAH in air
215
PM collected at a traffic site. Albinet et al. found that gasoline was an important source for
216
OPAHs, whereas Feilberg et al. stated that the most likely source for benzanthrone (BAQ) in
217
Kopenhagen was diesel vehicles (Ringuet et al., 2012a; Albinet et al., 2007; Feilberg et al.,
218
2001). The average concentration of AQ was in the range of the most abundant PAH
219
determined in this present study. Despite the lack of information on the sources of these
220
highly toxic compounds, gasoline and diesel combustion could be possible primary emission
221
sources of the OPAHs in the air PM of the Sulaimaniyah downtown area.
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3.3 Carcinogenic risk assessment of the DBPs
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Because of the high toxicity of the DBP isomers and because their concentrations in air were
224
only reported in a few studies, we investigated their influence on the assessment of the
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carcinogenic risks relative to B[a]P. There are, in principal, two methods that are applied for
226
the carcinogenic risk assessments of PAHs in air, i.e., the surrogate method using B[a]P as a
227
marker substance for the entire PAH mixture and the toxic equivalency factor (TEF) approach
228
in which B[a]P equivalent concentrations are derived from the multiplication of individual
229
PAH concentrations with their carcinogenicity relative to B[a]P (i.e., TEF values) (Pufulete et
230
al., 2004; Delgado-Saborit et al., 2011). B[a]P equivalent concentrations were calculated for
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the DBPs using the highest TEFs reported in the literature (Boström et al., 2002), shown in
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Table 6, to prevent any possible underestimation of the relative B[a]P equivalent
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234
DBPs were clearly for DB[a,l]P, which had a value similar to that of B[a]P. This result was in
235
accordance with previous studies, although higher values were reported for DB[a,l]P than for
236
B[a]P, as shown in Table 6. The concentrations determined for B[a]P in downtown
237
Sulaimanyah for the locations M, P, G and K were in the range of 1.3-6.9 ng/m3, as shown in
238
Table 2, which indicated that the calculation of an annual mean concentration would possibly
239
exceed the EU yearly target value of 1 ng/m3 (European Parliament and Council, 2004), the
240
Swedish target level for 2015 of 0.3 ng/m3 (Swedish Government, 2005) and the average of
241
0.25 ng/m3 for B[a]P in the United Kingdom (Coleman et al., 2001). However, this result
242
needs to be confirmed by an additional yearly PM10 measurement. A prerequisite for using
243
B[a]P as a marker for the carcinogenicity of the complex mixture of PAHs in air is that the
244
relative concentration profiles show high temporal and spatial stability. A high correlation
245
between the concentrations of B[a]P and the DBPs was shown in air PM collected throughout
246
a year in Rome by Menichini and Merli (Menichini and Merli, 2012). This correlation was
247
also investigated in the present study, and the correlation between the B[a]P concentrations
248
and the sum of the four DBP isomers was calculated, shown in Fig S1, resulting in a
249
correlation coefficient of R2 = 0.96. This result supported the findings of Menichini and Merli
250
of using B[a]P as a marker for the sum of the DBP isomer concentrations. The correlation
251
coefficients for the individual DBPs vs. B[a]P were 0.89, 0.96, 0.94 and 0.72 for DB[a,l]P,
252
DB[a,e]P, DB[a,i]P and DB[a,h]P, respectively.
253
4. Conclusions
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In total, 43 PAHs and 4 OPAHs were detected and quantified at five locations in the city of
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Sulaimaniyah, Iraq for the first time. This study is, to our knowledge, the first to report
256
concentrations of DBPs and OPAHs in air PM10 from Iraq. The average level of the
257
carcinogenic PAH B[a]P in Sulaimaniyah PM10 was higher than the legislated EU target value
258
by a factor of three. The average level of this compound was even higher than previous
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Sweden and Rome, Italy. A strong linear correlation was found between the B[a]P and DBPs,
261
which supports the use of B[a]P as a marker in risk assessments. Among the 4 OPAHs, AQ
262
accounted for more than 60 % at each sampling location. OPAHs, especially AQ, were
263
considered mutagenic, and they were mostly associated with fine particles, which is why it is
264
important to perform additional studies on localizing the source and formation of OPAHs in
265
Sulaimaniyah air. The air in Sulaimaniyah is very polluted and most likely negatively affects
266
the health of its inhabitants. These results highlight the fact that more investigations need to
267
be performed on the formation and sources of the PAC in ambient air and their correlation
268
with the local and foreign sources because of their potential toxicity and the lack of data.
269
5. Acknowledgement
270
Billy Sjövall at SLB-analys, Stockholm, is acknowledged for lending us the PM10 sampling
271
equipment, Shaafan M. Hamza from Asia clinical lab is acknowledged for assisting with the
272
sampling.
273
Ioannis Sadiktsis for his comments on this manuscript. This study was financed by Stockholm
274
University and University of Sulaimaniyah.
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6. References
276 277 278 279 280
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Table 1. Sampling sites, abbreviations, date and duration.
Mawlawy street
M1
131226
10:24 Am, 6 h
Mawlawy street
M2
131227
10:08 Am, 6 h
Piramerd street
P1
131228
10:48 Am, 6.25 h
Piramerd street
P2
131229
10:55 Am, 6 h
Goran street
G1
131230
11:05 Am, 6 h
Goran street
G2
131231
11:10 Am, 5.75 h
Twimalik(roof)
T1
140102
05:55 Pm, 4.25 h
Twimalik (roof)
T2
140103
12:08 Am, 5.5 h
Twimalik (roof)
T3
140103
06:40 Pm, 5 h
Kawa street
K1
140104
10:13 Am, 5.5 h
Kawa street
K2
140105
10:10 Am, 5.5 h
Latitude
Longitude
35° 33' 21.51" N
45° 26' 12.55"E
35° 33' 29.94 N
45° 26' 38.53"E
35° 33' 25.75" N
45° 26' 41.86"E
35° 33' 53.68" N
EP AC C
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Start time and Duration
SC
Sampling date
45° 27' 4.807"E
M AN U
Abbreviation
35° 33' 12.9" N
TE D
Sampling site
45° 26' 22.68"E
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Table 2. PAH concentrations (pg/m3) in Sulaimaniyah city. G2 1110 282 785 1050 158 759 776 492 272 206 1040 3320 5240 444 358 228 366 485 456 2860 369 205 463 2432 130 191 212 92.7 2480 1120 2990 2880
T1 1200 220 372 486 87 309 353 246 416 290 541 2760 3500 576 427 266 289 366 422 1700 421 93 564 2770 212 176 223 88 3290 1660 3100 3550
T2 680 105 226 214 13 168 178 113 191 51 279 1550 1870 254 193 104 130 184 167 930 255 56.1 192 1390 50.4 68.7 68.2 36.8 1340 689 1270 901
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G1 4600 618 2810 3520 700 2760 2401 1130 821 595 3350 6070 8540 923 643 676 360 984 1120 4260 1020 430 1200 5520 261 405 471 203 5210 2510 5310 6860
SC
P2 12000 1750 6110 7490 1790 4220 4410 1870 254 471 484 1760 2570 386 275 181 413 467 431 1470 329 96.6 369 1900 222 175 179 81.3 2040 784 2210 2180
M AN U
P1 1490 235 467 595 153 330 374 272 287 128 455 2200 2790 289 266 195 108 323 340 1590 364 100 455 2270 169 197 208 97.0 2380 1010 2535 2910
TE D
M2 21803 3460 6410 7780 2080 3860 5160 4240 387 176 518 2800 3680 430 391 257 429 475 516 2180 497 88.5 645 3030 197 252 267 126 2730 1370 3340 3700
EP
M1 945 108 451 561 101 288 325 146 204 69 561 1470 2050 287 244 165 332 369 359 1620 369 88.9 374 1830 124 183 173 72.3 1760 866 2320 2130
AC C
Compound Phenanthrene Anthracene 3-Methylphenanthrene 2-Methylphenanthrene 2-Methylanthracene 9-Methylphenanthrene 1-Methylphenanthrene 4H-cyclopenta[def)phenanthrene 2-Phenylnaphthalene 3,6-Dimethylphenanthrene 3,9-Dimethylphenanthrene Fluoranthene Pyrene 1-Methylfluoranthene Benz[a]fluorene Benz[b]fluorene 2-Methylpyrene 4-Methylpyrene 1-Methylpyrene Benzo[ghi]fluoranthene Benzo[c]phenanthrene Benzo[b]naphto[1,2-d]thiophene Benz[a]anthracene Chrysene 3-Methylchrysene 2-Methylchrysene 6-Methylchrysene 1-Methylchrysene Benzo[b]fluoranthene Benzo[k]fluoranthene Benzo[e]pyrene Benzo[a]pyrene
T3 671 100 102 126 5.90 77.3 96.2 88.8 128 27.9 114 1030 1130 121 84.9 48.8 60.2 83.6 92.0 523 140 28.6 65.9 738 46.3 32.2 27.8 18.3 764 375 782 295
K1 723 101 208 275 34.9 160 186 138 143 57.5 208 1330 1720 227 191 193 171 206 186 1460 277 68.8 241 1630 86.9 119 114 60.4 1780 750 1940 1330
K2 1120 192 475 585 109 344 401 361 202 123 489 2410 3870 444 356 230 376 501 476 3400 540 170 659 3850 206 242 279 133 4010 1790 4300 3860
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265 73.5 1210 41.6 83.0 1820 25 114 1480 49.9 29.0
800 183 3250 116 215 4200 58 341 3095 119 56.0
2.63 x 104
9.06 x 104
3.20 x 104
6.50 x 104
11.4 x 104
397 78.3 1820 45.5 80.6 3120 20.5 113 2430 40.8 12.8
TE D EP
429 143 2130 81.9 156 2400 36.0 188 1560 61.4 31.0
105 59.5 764 26.5 59.2 802 15.0 216 593 24.5 15.3
31.8 37.0 258 16.3 33.9 480 6.00 46.3 377 17.2 < LOD
165 64.7 1130 33.7 76.9 1830 18.2 94.8 1550 31.6 9.4
483 130 2440 71.1 146 3910 40.6 171 3350 78.5 20.7
3.80 x 104
1.6 4 x104
9.32 x 103
2.13 x 104
4.73 x 104
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336 86.1 1450 46.7 95.8 2080 22.5 140 1710 45.0 21.7
SC
446 96.7 1740 55.0 111 2870 27.0 187.0 2390 47.0 22.9
4.20 x 104
M AN U
266 57.2 1130 35 60.0 1960 30.0 111.0 1630 41.2 31.8
AC C
Perylene Indeno[1,2,3-cd]fluoranthene Indeno[1,2,3-cd]pyrene Dibenz[a,h]anthracene Picene Benzo[ghi]perylene Dibenzo[a,l]pyrene Dibenzo[a,e]pyrene Coronene Dibenzo[a,i]pyrene Dibenzo[a,h]pyrene Sum PAH LOD = limit of detection
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Table 3. Average concentrations (pg/m3) of B[a]P, DB[a,l]P, DB[a,e]P, DB[a,i]P and DB[a,h]P determined in the present study and from literature data .
Italy, Rome
Brazil, Limeira
PM size PM10 PM10 PM1.5 PM1.5 PM2.5
Sub urbanb
2009
October- November
PM2.5
City, street
2010
City, traffic-residential area City, traffic-industrial area
2011
Spring, Autumn, winter Spring
NDR
January - December
2010
March
PM10
B[a]P 2020 953 714 23500 25000
DB[a,l]P 92 23.6 23 2869 NDR
EP AC C
City, trafficc
DB[a,i]P NDR NDR 15 6190 NDR
DB[a,h] P NDR NDR 53 9930 NDR
670
NDR
NDR
NDR
NDR
236
3.9
31
8.6
2.6
PM10
83
1.4
19
4.7
1.5
PM10
650
14
70
20
9
PM10
807
9.07
105
32.0
11.4
159
58
26
2013December-January PM10 3232 31 2014 NDR = no data reported, a= city center, b= 4 km away from city center, c=data from city center during day time
Iraq, Sulaimaniyah
DB[a,e]P NDR NDR 259 29300 NDR
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Season/Month Autumm, Winter Winter Summer Winter October- November
SC
Afganistan, Kabul Afganistan, Mazar e Sharif Sweden, Stockholm
Sub urbana
year 2008 2008 2007 2008 2009
M AN U
Sampling site City,traffic City,traffic City, roof
TE D
Country/City Portugal, Porto Portugal, Porto China, Beijing
Reference (Slezakova et al., 2011) (Slezakova et al., 2010) (Layshock et al., 2010) (Wingfors et al., 2011)
(Westerholm et al., 2012) (Menchini and Merli, 2012 (Jarvis et al., 2014) This study
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Table 4. OPAH concentrations (pg/m3) in Sulaimaniyah city. Sampling sites M1
M2
P1
P2
G1
9,10-Anthraquinone (AQ)
2380
3530
2440
1950
4257
4H-cyclopenta[def]phenanthren-4-one (CPPQ)
647
715
457
505
1170
Benzanthrone (BAQ)
815
840
637
616
2390
7,12-Benz[a]anthraquinone (BaAQ)
117
3.66 x 10
90.0 3
3.16 x 10
319 3
TE D EP
T1
T2
T3
K1
K2
1451
2118
1520
372
1950
2740
388
613
390
93
385
618
645
1180
469
127
692
1360
99.0
296
SC
5.27 x 10
126 3
8.13 x 10
3
2.58 x 10
M AN U
3.96 x 10
182 3
AC C
Sum OPAH
G2
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Compound, (Abbreviation)
3
4.21 x 10
3
94.0
2.47 x 10
30.0 3
6.20 x 10
151 2
3.18 x 10
285 3
5.00 x 103
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Table 5. Literature values of the OPAHs determined in this study in pg/m3. OPAH abbreviations are shown in Table 4. Year
Season/Month
PM
AQ
CPPQ
BAQ
BaAQ
Reference
Chile, Santiago
Urban
2000
Winter
PM10
1580
NDR
NDR
1370
(María del Rosario Sienra , 2006)
Urban
2000
Spring
PM10
560
NDR
NDR
470
Germany, Augsburg
Urban
2003/2004
Autum/ winter
PM2.5
1500
1200
NDR
NDR
(Schnelle-Kreis et al., 2009)
France, Marseilles
Urban
2004
July
PM10
1 398
NDR
219
120
(Albinet et al., 2007)
Afganstan ,Kabul
Urbana
2009
October- November
PM2.5
2500
2800
33000
3100
(Wingfors et al., 2011)
Afganistan, Masa-e Sharif
Urbanb
2009
October- November
PM2.5
460
420
6300
860
France, Paris
Traffic
2010
July
PM10
659.8
NDR
46.6
45.2
RI PT
Sampling site
M AN U
SC
Country/City
(Ringuet et al., 2012a)
AC C
EP
TE D
2013-2014 December-January PM10 2587 610 1000 171 This study Iraq, Sulaimaniyah City, trafficc NDR= no data reported, a= City center, b=4 km far away from city center, c= average concentration of OPAHs from city center during day time
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Limeria 807 907 105 320 114
SC
Rome 650 1400 70 200 90
M AN U
Stockholmb 83 140 19 47 15
TE D
Stockholma 236 390 31 86 26
EP
This work 3232 3008 159 580 260
AC C
Compound TEF 1 B[a]P 100 DB[a,l]P 1 DB[a,e]P 10 DB[a,i]P 10 DB[a,h]P a= 2010, b=2011
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Table 6. Average B[a]P equivalent concentrations [TEF x concentration] for B[a]P, DB[a,l]P, DB[a,e]P, DB[a,i]P and DB[a,h]P in Sulaimaniyah down town compared to values calculated from the literature concentration data presented in Table 3.
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AC C
EP
TE D
M AN U
SC
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HIGLIGHTS • The first reported air concentrations of PAHs and oxygenated PAHs in PM10 from Iraq • Mean benzo[a]pyrene concentration exceeded the EU target value • The dibenzopyrene and benzo[a]pyrene concentrations were highly correlated
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Electronic Supplementary Material Native and oxygenated polycyclic aromatic hydrocarbons in ambient air particulate matter from the city of Sulaimaniyah in Iraq
a
Unit of Analytical and Toxicological Chemistry,
RI PT
Trifa M. Ahmed, Baram Ahmed, Bakhtyar K. Aziz, Christoffer Bergvall and Roger Westerholm
Stockholm University SE-10691 Stockholm, Sweden
School of Science, Department of Chemistry,
University of Sulaimaniyah,
M AN U
b
SC
Department of Environmental Sciences and Analytical Chemistry,
Iraq, Kurdistan Region, Sulaimaniyah, P.O. Box: 170 Sulaimaniyah, Iraq *Corresponding author: Telephone: +46-(0)8-162440; Fax: +46-(0)8-156391;
TE D
Email: [email protected]
Table S1 List of PAH, OPAH standards and surrogate internal standards, supplier and purity Name Phenanthrene-D10
Supplier
Purity (%)
Chiron AS, Trondheim, Norwaya), Larodan Fine Chemicals AB,
99.3a), 97.2b)
EP
Sweden
b)
Merck, Germany
98.7
Anthracene
Sigma-Aldrich, St. Louis, MO, USA
99.6
3-Methylphenanthrene
Larodan Fine Chemicals AB, Sweden
99.9
2-Methylphenanthrene
Sigma-Aldrich, St. Louis, MO, USA
93.8
2-Methylanthracene
Koch-Light Laboratories, UK
100
9-Methylphenanthrene
Chiron AS, Trondheim, Norway
100
1-Methylphenanthrene
Larodan Fine Chemicals AB, Sweden
98.8
4H-Cyclopenta[def]phenanthrene
Sigma-Aldrich, St. Louis, MO, USA
99.1
3,6-Dimethylphenanthrene
Larodan Fine Chemicals AB, Sweden
96.1
2-Phenylnaphthalene
EGA-Chemie, Steinheim, Germany
94.2
9-Methylanthracene
Koch-Light Laboratories, UK
97.1
3,9-Dimethylphenanthrene
Chiron AS, Trondheim, Norway
99.7
Fluoranthene
Sigma-Aldrich, St. Louis, MO, USA
97.2
AC C
Phenanthrene
1
ACCEPTED MANUSCRIPT Chiron AS, Trondheim, Norwaya), Larodan Fine Chemicals AB,
Pyrene-D10
Sweden
99.8a), 95.7b)
b)
Janssen Chimica, Belgium
97.6
1-Methylfluoranthene
Chiron AS, Trondheim, Norway
99.7
Benzo[a]fluorene
Chiron AS, Trondheim, Norway
98.8
Benzo[b]fluorene
Sigma-Aldrich, St. Louis, MO, USA
99.1
2-Methylpyrene
Chiron AS, Trondheim, Norway
98.3
4-Methylpyrene
Chiron AS, Trondheim, Norway
1-Methylpyrene
Larodan Fine Chemicals AB, Sweden
Benzo[c]phenanthrene
Chiron AS, Trondheim, Norway
Benzo[ghi]fluoranthene
Larodan Fine Chemicals AB, Sweden
Benzo[b]naphto[1,2-d]thiophene
Chiron AS, Trondheim, Norway
99.6
Benz[a]anthracene-D12
Chiron AS, Trondheim, Norway
98.6
Benz[a]anthracene
Fluka AG, Switzerland
98.4
Chrysene
Sigma-Aldrich, St. Louis, MO, USA
96.4
3-Methylchrysene
Chiron AS, Trondheim, Norway
99.1
2-Methylchrysene
Chiron AS, Trondheim, Norway
99.7
6-Methylchrysene
Chiron AS, Trondheim, Norway
100
1-Methylchrysene
Chiron AS, Trondheim, Norway
99.3
Benzo[k]fluoranthene Benzo[e]pyrene
SC
M AN U
EP
Benzo[a]pyrene-D12
TE D
Benzo[b]fluoranthene
RI PT
Pyrene
99.6
99.1
99.5
99.5
Chem Service, West Chester, PA, USA
100
Chem Service, West Chester, PA, USA
98.3
Sigma-Aldrich, St. Louis, MO, USA
99.7
Chiron AS, Trondheim, Norwaya), Larodan Fine Chemicals AB,
98.7a), 98.1b)
Sweden
b)
Sigma-Aldrich, St. Louis, MO, USA
97.6
Perylene
Sigma-Aldrich, St. Louis, MO, USA
99.5
Indeno[1,2,3-cd]fluoranthene
Radiant Dyes, Wermelskirchen, Germany
98.4
Indeno[1,2,3-cd]pyrene
AccuStandard Inc., New Haven, CT, USA
99.8
Dibenz[a,h]anthracene
Fluka AG, Switzerland
99.4
Picene
Larodan Fine Chemicals AB, Sweden
96.1
Benzo[ghi]perylene-D12
Chiron AS, Trondheim, Norway
99.6
Benzo[ghi]perylene
Janssen Chimica, Belgium
98.8
Dibenzo[a,l]pyrene
AccuStandard Inc., New Haven, CT, USA
96
Dibenzo[a,e]pyrene
LGC Promochem, Sweden
98
Coronene-D12
Chiron AS, Trondheim, Norway
98.9
Coronen
Radiant Dyes. Wermelskirchen, Germany
100
AC C
Benzo[a]pyrene
2
ACCEPTED MANUSCRIPT Dibenzo[a,i]pyrene-D14
LGC Promochem, Sweden
98
Dibenzo[a,i]pyrene
Sigma-Aldrich, St. Louis, MO, USA
96.4
Dibenzo[a,h]pyrene
Koch-Light Laboratories, UK
100
Anthraquinone -D8
Chiron AS (Trondheim, Norway)
99.4
9,10-Anthraquinone
Chiron AS (Trondheim, Norway)
99.5
Cyclopenta[def]phenanthren-4-one Chiron AS (Trondheim, Norway) Chiron AS (Trondheim, Norway)
7,12 Benz[a]anthraquinone
Chiron AS (Trondheim, Norway)
99
98.5
97.5
M AN U
SC
Benzoanthrone
RI PT
OPAHs
700
600
EP
y = 0.0733x + 41.344 R² = 0.96
400
300
AC C
TDBP pg/m3
500
TE D
Fig S1. Correlation between concentration of B[a]P and total concentration of DBP isomers in PM10.
200
100
1000
2000
3000
4000
5000
6000
7000
8000
B[a]P pg/m3
3