Level, potential sources of polycyclic aromatic hydrocarbons (PAHs) in particulate matter (PM10) in Naples

Accepted Manuscript Level, potential sources of Polycyclic Aromatic Hydrocarbons (PAHs) in particulate matter (PM10) in Naples Paola Di Vaio, Beatrice Cocozziello, Angela Corvino, Ferdinando Fiorino, Francesco Frecentese, Elisa Magli, Giuseppe Onorati, Irene Saccone, Vincenzo Santagada, Gaetano Settimo, Beatrice Severino, Elisa Perissutti PII:

S1352-2310(16)30028-0

DOI:

10.1016/j.atmosenv.2016.01.020

Reference:

AEA 14400

To appear in:

Atmospheric Environment

Received Date: 12 October 2015 Accepted Date: 9 January 2016

Please cite this article as: Di Vaio, P., Cocozziello, B., Corvino, A., Fiorino, F., Frecentese, F., Magli, E., Onorati, G., Saccone, I., Santagada, V., Settimo, G., Severino, B., Perissutti, E., Level, potential sources of Polycyclic Aromatic Hydrocarbons (PAHs) in particulate matter (PM10) in Naples, Atmospheric Environment (2016), doi: 10.1016/j.atmosenv.2016.01.020. 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 Level, potential sources of Polycyclic Aromatic Hydrocarbons (PAHs) in particulate matter (PM10) in Naples Paola Di Vaioa, Beatrice Cocozziellob, Angela Corvinoa, Ferdinando Fiorinoa, Francesco Frecentesea, Elisa Maglia, Giuseppe Onoratib, Irene Sacconea, Vincenzo Santagadaa, Gaetano

a

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Settimoc, Beatrice Severinoa, Elisa Perissuttia,* Dipartimento di Farmacia, Università degli Studi di Napoli “Federico II”, Napoli, Italy

b

Agenzia Regionale per la Protezione Ambientale in Campania, Napoli, Italy

c

Reparto Igiene dell'Aria, Dipartimento Ambiente e Connessa Prevenzione Primaria, Istituto Superiore di Sanità, Italy

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* Corresponding Author. Tel: +39081678646. E-mail: [email protected]

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Keywords

Particulate Matter; PAHs; Principal component analysis; Diagnostic ratio; Toxic equivalent factors; Health risk assessment

ABSTRACT

In Naples, particulate matter PM10 associated with polycyclic aromatic hydrocarbons (PAHs) in

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ambient air were determined in urban background (NA01) and urban traffic (NA02) sites. The principal objective of the study was to determine the concentration and distribution of PAHs in PM10 for identification of their possible sources (through diagnostic ratio - DR and principal component analysis - PCA) and an estimation of the human health risk (from exposure to airborne

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TEQ). Airborne PM10 samples were collected on quartz filters using a Low Volume Sampler (LVS) for 24 h with seasonal samples (autumn, winter, spring and summer) of about 15 days each between

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October 2012 and July 2013. The PM10 mass was gravimetrically determined. The PM10 levels, in all seasons, were significantly higher (P<0.001) in the urban-traffic site (NA02) than in the urbanbackground site (NA01). The filters were then extracted with dichloromethane using an ultrasonicator (SONICA) to perform a detailed characterization of 12 priority PAHs proposed by the USEPA, by gas chromatography-mass spectrometer (GC-MS) analysis. The concentration of Benzo[a]Pyrene, BaP (EU and National limit value: 1 ng m-3 in PM10), varied from 0.065 ng m-3 to 0.872 ng m-3 in spring time (NA01) and from 0.120 ng m-3 during autumn time to 1.48 ng m-3 of winter time (NA02) with four overshoots. In NA02 the trend of Σ12 PAHs was comparable to NA01 but were observed higher values than NA01. In fact, the mean concentration of Σ12 PAHs, in urban-traffic site was generally 2 times greater than in urban-background site in all the campaigns. 1

ACCEPTED MANUSCRIPT PAHs with 5 and 6 ring, many of which are suspected carcinogens or genotoxic agents, (i.e Benzo[a]Pyrene,

Indeno[1,2,3-cd]Pyrene,

Benzo[b]Fluoranthene,

Benzo[k]Fluoranthene

and

Benzo[g,h,i]Perylene), had a large contribution (~50-55 %) of total PAHs concentration in PM10 in two sites and in each of the campaigns. Diagnostic ratio analysis and PCA suggested a substantial contributions from traffic emission with

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minimal influence from coal combustion and natural gas emissions. In particular diesel vehicular emissions were the major source of PAHs at the studied sites. The use of Toxicity Equivalence Quantity (TEQ) concentration provide a better estimation of carcinogenicity activities; health risk to adults and children associated with PAHs inhalation was assessed by taking into account the lifetime average daily dose and corresponding incremental lifetime cancer risk (ILCR). The ILCR

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was within the acceptable range (10−6 to 10−4), indicating a low health risk to residents in these

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areas.

1. Introduction

Atmospheric aerosols (or particulate matter, PM) are classified as carcinogenic. While air pollution is a complex mixture of many gases and compounds, PM in the air has been particularly identified as the main component causing the cancer (IARC, 2013).

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The PM10 fraction of aerosols is defined as the particulate matter which passes through a sizeselective inlet as defined in the reference method for the sampling and measurement of PM10, EN 12341, with a 50% efficiency cut-off at 10 µm aerodynamic diameter (directive 2008/50). It is a complex mixture of elemental and organic carbon (e.g. PAHs), ammonium, nitrates, sulphates,

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mineral dust, trace elements and water. It may be of natural or anthropogenic origin and can be emitted directly into atmosphere from gaseous precursors (Putaud et al. 2010). Owing to the potential adverse health and environmental impacts, legislation of the PM10

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concentration limits has been established in many region of the world including the European Union (Kocak et al., 2009). The annual and daily PM10 values have been limited to 40 µg/m3 and 50 µg/m3 (which may only be exceeded for 35 days), respectively addressed by Directive 2008/50/EC on ambient air quality and National Legislation Decree N. 155/2010. Polycyclic aromatic hydrocarbons (PAHs) are semi-volatile organic compounds consisting of only carbon and hydrogen with a fused ring structure containing at least two benzene rings (Ravindra et al., 2008). Some PAHs are a major group of carcinogens, mutagens and teratogens present in the environment. They are products of incomplete combustion of organic material, released from both natural (forest fires and volcanic eruption) and anthropogenic sources. Sources of PAHs contamination in the atmosphere include domestic and industrial coal combustion, biomass 2

ACCEPTED MANUSCRIPT combustion, and emissions from road vehicles (Heywood et al., 2006). PAHs are distributed in the atmosphere between gas and particulate phases, depending on the volatility of the PAHs species. Higher condensed molecules with four and more rings are found mainly in the particulate phase whereas low molecular weight or 2–3 ring PAHs form dominantly in the gas phase (Ravindra et al., 2008; Hanedar et al., 2011). The highest levels of PAHs concentration in both gas and particulate

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phases can be found in urban areas with high vehicular traffic activities and dispersion of the atmospheric pollutants (Hanedar et al., 2011; Harrison et al., 1996; Lim et al., 1999; Tavares et al., 2004; Ravindra et al., 2008).

In the atmosphere, they can undergo degradation by photochemical reactions and they can deposit

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on the ground, both by dry and/or wet deposition. Reaction rates, mechanisms and products of the overall phenomenon depend not only on oxidant levels, radiation intensity and the structure of specific PAHs but also on the physical and chemical surface properties of the particles, on/in which

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the PAHs are located.

One of the main concerns of the human exposure at PAHs is due to their carcinogenic and mutagenic properties (Boström et al. 2002; Bourotte et al. 2005; Ravindra et al. 2006). Most of the probable human carcinogenic PAHs are found to be associated with particulate matter (Callén et al. 2008), especially in fine mode particles in ambient air (Ravindra et al. 2008). For this

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reason, humans are exposed to PAHs mainly through respiratory tract, although PAHs can enter an organism through the digestive tract following intake of food containing PAHs (e.g. grilled meat or vegetables grown near areas with intense traffic) or through the skin by contact with derivate of petroleum (tar, pitch and et cetera). Once inside, PAHs can be transformed into reactive

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electrophilic intermediates that can form adducts with DNA, RNA and proteins, and induce mutations which can cause tumors in several organs (the lungs, the esophagus, the colon, the pancreas, the skin, the bladder and et cetera) (Boström et al. 2002). The IARC (International

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Agency for Research on Cancer) has classified several PAHs with respect to their carcinogenicity to humans, inclusive of: BaP (group 1 toxic, carcinogenic); DbA (group 2A, probably carcinogenic); BbF, BkF, BjF, BaA, Chry, Ind (group 2B toxic, possibly carcinogenic to humans) and Fla, Cor, Pyr and BPer (group 3, carcinogenicity not classifiable) (IARC 2012). In order to establish a metric that estimates the total carcinogenic potential of atmospheric PAHs, the concept of Toxicity Equivalent Factor (TEFs) was established, whereby the toxicity of several PAHs species has been quantified with respect to BaP, a reference specie with well-characterized toxicity (Nisbet and LaGoy 1992; Larsen and Larsen 1998) compared with Directive 2004/107/EC, which establishes a target value of exposure only for BaP (annual average of 1 ng m-3 sampled in the PM10 size fraction). 3

ACCEPTED MANUSCRIPT The TEQ calculation which is based on the toxic equivalent factors (TEF), proposed by Nisbet and Lagoy (1992) and USEPA (2005), can be used to estimate occupational and environmental health risks associated with exposure of PAHs-bound PM10. According to our knowledge, this is the first time that PM10-bound PAHs are determined in the area of Naples. The main objectives of the research are: (i) to analyze concentration and seasonal

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variations of PM10-bound PAHs at two sites located in Naples, (ii) to estimate the human health risk from PAHs based on the TEQs and the inhalation cancer risk (ICR) and (iii) to identify possible sources of PM10-bound PAHs using correlations as diagnostic ratios (DRs) and principal component

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analysis (PCA) (Guo et al., 2003; Li et al., 2006; Andreou and Rapsomanikis, 2009).

2. Experiment 2.1. Sampling sites description

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Naples (40°50’00’’N, 14°15’00’’ E) is a Mediterranean coastal city, with one of the highest population density in Italy and Europe (8220 habitants/km2). It is extended on an area of 119.02 Km2, in which many buildings are located and it is characterized by a marked vehicular traffic. It looks to the sea with an harbor that welcomes a lot of ships during the year, not only merchant but also cruise ones, especially during summer season. In addition, Naples presents an international

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airport, whose important characteristic is its position in the middle of its centre. Regarding industrial sector, there are some little and medium factories, such as those producing Porcelain, and they are located in its centre and in the first areas around it. The locations of the sampling sites are shown in Fig.1. The urban-background site (NA01), selected

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as a control to monitor the hypothetical background level of pollution, was located in the Astronomical Observatory (14°15'5.54''E, 40°51'12.74''N), a green area in short distance from a heavily busy road (Tangenziale). Therefore, this site is indirectly influenced by traffic or other

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emissions (e.g. ceramic industry of Capodimonte). The sampling system was situated in a green area 1.5 m above ground level. The urban-traffic site (NA02) was located in central Naples (40°51’12.47’’N, 14°15’54’’ E), at 2 Km away from NA01 site and 1 Km away from the Naples harbor. This site is characterized by presence of commercial shops, restaurants, pizzerias, narrow streets and high traffic density. The sampling equipment was placed near a crossroad, 1.5 m above ground level. Both sampling equipment were the property of the Regional Environmental Protection Agency (ARPAC). The climate of Naples is temperate, strongly influenced by the sea breeze. The average annual precipitation is about 100 mm, mean monthly values of relative humidity during the sampling campaigns ranged between 50% and 75%, while those of temperature between 6°C and 30 °C. 4

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ACCEPTED MANUSCRIPT

Fig.1 Location of sampling sites, Urban-background site (NA01) and Urban-traffic site (NA02).

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ACCEPTED MANUSCRIPT 2.2 PM sampling and mass measurement PM10 sampling was carried out concurrently at the two sites (NA01, NA02) during autumn time (16 October - 11 November 2012), winter time (01 March - 15 March 2013), spring time (28 May - 11 June 2013) and summer time (16 July – 30 July 2013). Twenty-four hour samplings were carried out according to EN-12341 using for each site Low Volume PM10 Samplers (Skypost, TCR Tecora,

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Italy) with flow rate 2.3 m3 h-1 operating in parallel at each site. PM10 was collected on high purity quartz filter (Frisinette APS, 47 mm) pre-fired (500°C for 4h). The sampling campaigns resulted in the collection of 27 (autumn time), 13 (winter time), 15 (spring time) and 15 (summer time) valid samples at the Urban-background site (NA01) and 25 (autumn time), 15 (winter time), 15 (spring

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time) and 15 (summer time) valid samples in the urban site (NA02). Samples considered not valid were mostly due to technical problems with the samplers, which resulted in short sampling times. The PM10 mass was gravimetrically determined according to UNI EN-12341. Loaded and unloaded

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filters were conditioned for 48 h at 20±1 °C and 50±5 °C relative humidity before weighing in a Sartorius SE 2-F microbalance (Readability: 0.1 µg). Filter samples were stored on petri dishes in a cool and dark place until analyses (for less than one week). Field blank filters were used to correct the eventual systematic errors and to evaluate measurement uncertainty through the statistical

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analysis of blanks (Park et al. 2002).

2.2. Sample extraction and PAHs analysis

The samples were extracted in 25 mL dichloromethane using an ultrasonicator (SONICA®) for 30 minutes at controlled temperature (~10 °C). The extracted solutions were then filtered for the

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removal of any remaining insoluble particles through a 45 µm nylon filter prior to being evaporated by vacuum rotary until they were nearly dried by a moderate flow of nitrogen. The mixture of

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internal standards (acenaphthene-d10, phenanthrene-d10 and pyrylene-d12, o2Si, USA) 0.5 mL of 0.5 µg mL-1 was spiked into the extracted solution. The rate was analyzed with a Agilent 6890, U.S.A. gas chromatography-mass spectrometer (GC-MS) with automatic injection, working under the following conditions: (a) 2µL splitless injection to 280 °C of injection temperature; (b) capillary column HP-5MS 30 m x 0.25 mm x 0.25µm film thickness; (c) helium as carrier gas with a purity of 99.9% at a constant flow of 1 mL min-1; (d) heating programmed: 110-310 °C (110 °C hold time of 1 min, 110 °C to 180 °C 25 °C min-1, 180 °C to 280 °C 5 °C min-1 hold time for 7.20 min, 280 °C to 320 °C 5 °C min-1 hold time for 2 min), run time of 45 min; (e) acquisition mode, electron impact (EI) at 70 eV. The detection mode was operated in selective ion monitoring (SIM). Target compounds were identified by comparison of retention time and mass spectra to those of authentic external standards (Guo et al 2009). Compounds including sixteen polycyclic aromatic 6

ACCEPTED MANUSCRIPT hydrocarbons (o2Si, USA) (Naphthalene (Nap), Acenaphthylene (Acy), Acenaphthene (Ace), Fluorene (Flu), Phenanthrene (Phe), Anthracene (Ant), Fluoranthene (Fla), Pyrene (Pyr), Benz[a]Anthracene (BaA), Chrysene (Chr), Benzo[b]Fluoranthene (BbF), Benzo[k]Fluoranthene (BkF), Benzo[a]Pyrene (BaP), Indeno[1,2,3-cd]Pyrene (Ind), Dibenzo[a,h]anthracene (DbA) and Benzo[g,h,i]perylene (BPer)) but only the 12 PAHs of sanitary and hygienic interest were identified

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in each sample. Difficulties were often associated with the GC separation of BbF and BkF and since Benzo[k]fluoranthene co-eluted with BbF (Pietrogrande et al. 2014), the sum of these isomers was

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used as an abbreviation, B(b+k)F. All results were expressed in ng m-3.

2.3. Quality control

Quantification was performed using internal standard calibration method (six-point calibration), and

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the correlation coefficients (r2) for the calibration curves were all greater than 0.995. Surrogate standard solution mentioned (internal standard) was added the calibration standard with the same concentration as it was used for the sample analysis. Analytical method was checked for precision and accuracy. Limits of detection (LOD) were calculated based on 3SD/S (SD is the standard deviation of the response of seven replicate standard solution measurements and S is the slope of

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the calibration graph). LODs of PAHs were in the range of 0.003–0.360 ng m-3 (Table 1). Blank filters were prepared and analyzed together with the samples, verifying that the PAHs values were under the LODs. Efficiency of PAHs analysis method was tested by using spike method. For spike method, 1 mL of 1 µg mL-1 of mixed 16 PAHs standard solution (O2Si) was spiked on a quartz

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fiber filter (Wiriya et al 2013). Recoveries of PAHs from spike method (n=3) were 58 to 99% (Table 1). For every batch of ten samples, a method blank (solvent) and a spiked blank (internal standards spiked into solvent) were analyzed. Blanks that were run periodically contained an

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undetectable amount of target analytes. The coefficients of variation of PAHs concentration in duplicate samples were less than 15 %.

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ACCEPTED MANUSCRIPT Table 1 Limits of detection (LODs) of PAHs analyzed by GC-MS and Recovery values after extraction. PAHs

Abbrevation

Ring number

LOD (ng m-3) Recovery±SD(%)

Nap

2

0.006

65±6

Acenaphthylene

Acy

3

0.005

72±6

Acenaphthene

Ace

3

0.006

68±6

Fluorene

Flu

3

0.004

78±8

Phenanthene

Phe

3

0.360

60±5

Anthracene

Ant

3

0.020

95±7

Fluoranthene

Fla

4

0.008

58±13

Pyrene

Pyr

4

0.003

72±12

Benzo(a)anthracene

BaA

4

0.007

72±8

Chrysene

Chr

4

0.005

83±8

0.006

63±11

Benzo (a)pyrene

BaP

5

Indeno (1,2,3-cd) pyrene

Ind

5

Dibenzo(a,h)anthracene

DbA

6

Benzo(g,h,i)perylene

BPer

6

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5

0.003

99±11

0.003

77±13

0.006

70±14

0.006

87±14

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Benzo(B+K) Fluoranthene B(b+k)F

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Naphthalene

3. Results and discussion 3.1. PM10 mass concentrations

Summary data of PM10 mass concentrations (minimum, maximum and mean) determined at the two

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sampling sites are reported in Table 2. Table 2

PM10 mass concentration at two sites in µg m-3

Urban – traffic site (NA02)

Winter

Spring

Summer

Autumn

Winter

Spring

Summer

27

13

15

15

25

15

15

15

Min

18.6

15.0

13.9

25.0

33.1

16.8

14.8

35.0

Max

46.7

53.2

29.8

53.7

68.2

59.1

31.8

51.3

26.1

26.4

20.8

29.9

45.3

38.2

26.1

41.9

0

0

1

10

3

0

0

mean

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Autumn samples no.

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Urban - backgroundsite (NA01)

no.exceeding 0

The PM10 levels, in all seasons, were significantly higher (P<0.001) in the urban-traffic site (NA02) than in the urban-background site (NA01). These results reflect a higher emissions at site NA02 probably due to the nearby densely trafficked roads. The seasonal differences of PM10 concentrations at the two sites were not statistically significant. Only in urban-traffic site (NA02) elevated concentrations were found during autumn time with the 40% of exceedances of the 24-h (50 µg m-3 daily limit of the Italian Legislative Decree N. 155 “Implementation of the 2008/50/EC Directive on Ambient Air Quality and Cleaner Air for Europe”). 8

ACCEPTED MANUSCRIPT 3.2 PAHs levels Summary data (minimum, maximum and mean) of 12 PAHs concentration determinate in PM10 air samples are reported in Tables 3 and 4 for the Urban-background site (NA01) and Urban-traffic site (NA02) respectively. For data below the detection limit, the value was calculated as half detection limit, itself has been

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used to calculated the mean and total concentrations (Nesta Bortey- Sam et al. 2015). Table 3

PAHs concentration determined in atmospheric PM10 at Urban-background site (NA01) in ng m-3

Mean

Mean

Max

Min

Phe

0.378 1.513 0.180 0.617

1.25

0.264 0.224 0.750 0.034 0.404 0.835 0.180

Ant

0.044 0.336 0.010 0.107 0.650 0.010 0.010 0.010 0.010 0.075 0.139 0.010

Fla

0.177 1.643 0.003 0.032 0.110 0.004 0.073 0.198 0.004 0.265 0.514 0.111

Pyr

0.206

BaA

0.116 0.805 0.003 0.058 0.250 0.004 0.060 0.378 0.004 0.329 0.536 0.163

Chr

0.266 0.935 0.003 0.196 0.680 0.005 0.070 0.440 0.003 0.217 0.268 0.158

B(b+k)F

0.648 1.970 0.216 0.375 0.980 0.120 0.139

BaP

0.246 0.513 0.065 0.400 0.587 0.220 0.271 0.872 0.069 0.401 0.544 0.245

Ind

0.179 0.516 0.001 0.191 0.321 0.072 0.076 0.940 0.001 0.001 0.001 0.001

DbA

0.035 0.396 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003

BPer

0.270 0.651 0.003 0.422

1.12

0.003 0.097 1.168 0.003 0.003 0.003 0.003

Σ12PAHs

2.56

6.95

0.751

1.00

Max

Min

Mean

Max

Min

0.046 0.090 0.202 0.001 0.376 0.711 0.220

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0.001 0.277

10.71 0.488

Table 4

Mean

Summer

PAHs

1.43

Min

Spring

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Max

Winter

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Autumn

2.68

1.11

1.05

6.02

0.003 0.336 0.447 0.157

0.135

2.41

4.00

1.20

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PAHs concentration determined in atmospheric PM10 at Urban-traffic site (NA02) in ng m-3

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Autumn

Spring

Mean Max

Min

Summer

PAHs

Mean Max

Phe

0.855 2.649 0.180 1.11

2.41

0.758 0.493 0.822 0.180 0.459 0.800 0.180

Ant

0.054 0.209 0.010 0.184 1.50

0.010 0.010 0.010 0.010 0.035 0.183 0.010

Fla

0.359 0.915 0.047 0.564 1.07

0.004 0.130 0.201 0.082 0.214 0.318 0.132

Pyr

0.580 1.08

BaA

0.283 0.648 0.003 0.187 0.360 0.065 0.194 0.399 0.113 0.236 0.358 0.153

Chr

0.529 1.28

B(b+k)F

1.22

BaP

0.525 1.06

0.120 0.920 1.48

0.564 0.393 0.650 0.280 0.663 1.049 0.475

Ind

0.494 1.09

0.107 0.571 1.26

0.176 0.319 0.663 0.200 0.121 0.878 0.001

DbA

0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003

BPer

0.965 1.932 0.287 0.957 1.71

Σ12 PAHs 5.87

Min

Winter

Mean Max

Min

Mean Max

Min

0.119 0.538 0.800 0.220 0.134 0.180 0.102 0.294 0.451 0.191

0.003 0.397 0.670 0.175 0.196 0.538 0.096 0.227 0.325 0.177

2.442 0.003 0.597 1.13

13.31 0.882 6.03

0.215 0.265 0.596 0.035 0.675 1.356 0.216

0.258 0.636 1.072 0.358 0.248 0.904 0.003

12.40 2.45

9

2.77

5.13

1.46

3.18

6.63

1.54

ACCEPTED MANUSCRIPT The Benzo[a]pyrene (BaP) has been regarded as a marker of total PAHs and carcinogenic PAHs

(EC, 2001) and its annual target value in PM10 set by the European Commission (directive 2004/107) and Italian Legislative Decree N. 155/2010 (“Implementation of the 2008/50/CE Directive 2008/50/CE on Ambient Air Quality and Cleaner Air for Europe”) is 1 ng m-3. In this study, in NA01 the PM10-BaP concentrations of the campaigns varied from 0.065 ng m-3 to

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0.872 ng m-3 during spring time (Table 1). In NA02, the PM10-BaP concentrations varied from 0.120 ng m-3 during autumn time to 1.48 ng m-3 of winter time (Table 2) with four overshoots. The sum of concentrations of 12 PAHs (Σ12PAHs: Phe, Ant, Fla, Pyr, BaA, Chr, B(b+k)F, BaP, Ind, DbA, BPer) in air samples (PM10) in urban-background site (NA01) ranged from 0.135 ng m-3

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(min.) to 10.71 ng m-3 (max). In NA02 the value ranged from 0.882 ng m-3 (min.) to 13.31 ng m-3 (max).

In NA02 the trend of Σ12 PAHs was comparable but were observed higher values than NA01. In

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fact, the mean concentration of Σ12 PAHs, in urban-traffic site was generally 2 times greater than in urban-background site in all the campaigns. This could be attributed to the fact that sampling in NA02 site was performed in a traffic area suffering high exhaust emission and hosting small industrial activities (e.g pizza restaurant). Considering that during the summer the photodegradation is higher than spring, because the temperature were higher, was interesting to note that

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the mean concentration of Σ12PAHs in this season, was greater than spring. The large concentration of Σ12 PAHs in summer in both site, probably can be due to a greater number of cruise ships docked in the Naples harbor during this season.

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3.3 Most abundant PAHs in air

The relative contribution (%) of individual PAH in total amount of 12 PAHs in PM10 of all the

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campaigns is presented in Figures 2 and 3 for urban-background site (NA01) and urban-traffic site (NA02) respectively.

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ACCEPTED MANUSCRIPT 100 BPer 90

Dba

80

Ind

70

BaP

60

B(b+k)F

50

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Chr

40

BaA

30

Pyr

20

Fla

10

Ant

0

Autumn

Winter

Spring

Phe

Summer

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Season

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% c o n t r i b u t i o n

Fig. 2.The relative contribution (%) of individual PAH in total PAHs in PM10 in NA01. For abbreviation of PAHs, see Table 1.

100 90

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Dba 80 70

50 40 30

BaP B(b+k)F

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60

Ind

Chr BaA Pyr

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% c o n t r i b u t i o n

BPer

20

Fla

10

Ant Phe

0

Autumn

Winter

Spring

Summer

Season Fig. 3.The relative contribution (%) of individual PAH in total PAHs in PM10 in NA02. For abbreviation of PAHs, see Table 1.

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ACCEPTED MANUSCRIPT The distribution of carcinogenic PAHs (BaA, Chr, B(b+k)F, Ind, BaP, DbA), and non carcinogenic PAHs (Phe, Ant, Fla, Pyr, BPer) in PM10 was quite similar for both sites (NA01 and NA02) in all the campaigns. Benzo(a)Pyrene (BaP) and Benzo(B+K)Fluoranthene (B(b+k)F) seem to be the best representative of all carcinogenic PAHs, everyone represented 15-16% of PAHs in mean during year. A commune

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feature for all the campaigns was that the most abundant non carcinogenic PAHs (Phe, Ant, Fla, Pyr, BPer) in PM10 were Phenanthrene (Phe) and Pyrene (Pyr), both of them representing 15-16% of PAHs, in mean during year. Anthracene (Ant) was the least abundant with a concentration below detection limit in almost all samples.

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The 12 PAHs considered can be classified into 3 groups, including 3 ring (Phe and Ant), 4 ring (Fla, Pyr, BaA and Chr) and sum of 5and 6 ring (BaP, Ind, DbA, BPer, BbF and BkF,) PAHs. The relatively importance of three groups of PAHs in four seasons in NA01 and NA02 sites is

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shown in Table 5.

Table 5

The relative contribution (%) of different ring groups in 12 PAHs at different seasons in NA01 and NA02 sites.

Urban - background site (NA01)

Autumn Winter Spring Summer Autumn Winter Spring Summer

TE D

PAHs

Urban – traffic site (NA02)

3 ring

16.45

27.06

21.01

19.90

15.49

21.44

17.88

15.54

4 ring

29.84

21.01

26.31

49.29

29.85

27.99

23.67

30.58

5+6 ring

53.71

51.93

52.67

30.93

54.66

50.57

58.45

53.88

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The most prominent groups of PAHs in PM10 of the autumn, winter, spring and summer campaigns of NA01 and NA02 were the larger 5 and 6 rings PAHs. The relative concentration of 5 and 6 rings

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PAHs was constant in the four seasons in both sites NA01 and NA02 (~50-55 %). Only during the summer in NA01 was observed a reduction of 20% respect to the other seasons. The sum of 5 and 6 ringPAHs are mainly in particle phase during the year. In both sites the 3 ring PAHs were only a small part in 12 PAHs (generally less than 20%) because they are primarily in gas phase even in winter owing to their high volatility (Simoneit et al. 1986). The relative concentration of 4 ring PAHs for both sites was generally less than 30%, only in summer in NA01 site, was observed a value of 49%. In NA01, to the increased concentration of 4 ring PAHs corresponds a decreased concentration of 5 and 6 ring PAHs; a similar trend was not observed during the summer in NA02. Considering that the presence of 3 ring PAHs may be attributed to combustion at low temperatures and in these conditions 4 ring PAHs are abundant (Lake et al. 1979) too, while at high temperature 12

ACCEPTED MANUSCRIPT combustion 5 and 6 ring PAHs are dominant (Laflamme and Hites 1978). According to these results, it is possible to deduce that ~55 % of PAHs in Naples were released by high-temperature combustion sources and the per cent value is in accordance with Knust (Nesta Bortey et al 2015).

3.4 Correlations between PM10 and PAHs

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Pearson correlations of PM10, total PAHs (tPAHs), non carcinogenic PAHs (ncPAH) (Phe, Ant, Fla, Pyr, BPer) and carcinogenic PAHs (cPAH) (BaA, Chr, B(b+k)F, Ind, BaP, DbA), are shown in Tables 6-7 for urban-background site (NA01) and urban-traffic site (NA02).

Table 6

Autumn

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Pearson correlations of PM10 concentrations in NA01 (in each sampling period) Winter

Spring

Summer

tPAH

1

ncPAH 0.797 cPAH

0.797 0.942 1

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tPAH ncPAH cPAH tPAH ncPAH cPAH tPAH ncPAH cPAH tPAH ncPAH cPAH 1

0.945 0.956

0.945

0.942

1

1 0.817 0.919

1 0.956

0.817

Correlation is significant at the 0.05 level

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Table 7

1 0.982

0.919 0.982

1

0.878

1 0.848 0.878

1

0.848

1

1

Pearson correlations of PM10concentrations in NA02 (in each sampling period) Autumn

Winter

Spring

Summer

tPAH ncPAH cPAH tPAH ncPAH cPAH tPAH ncPAH cPAH tPAH ncPAH cPAH 1

ncPAH 0.942 cPAH

0.938

0.942 0.938

1

1 0.768 0.867

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tPAH

0.768

0.867 0.813

1

1

1 0.813

0.747 1

1 0.747

1

0.930 0.931

0.930

1 0.732

1 0.931

0.732

1

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Correlation is significant at the 0.05 level

In NA01 and in NA02 the PM10 concentrations were not significantly correlated (<0.70) with all forms of PAHs (tPAHs, cPAHs and ncPAHs). In NA01, the better correlation (>0.70) could be founded during each season between tPAH and ncPAH, while in NA02, a considerable correlation (>0.70) was founded between tPAH and cPAH. These results could be assumed that cPAHs most influenced the urban-traffic site (NA02).

13

ACCEPTED MANUSCRIPT 3.5 Toxicity equivalent quantity concentration (TEQ) of PAHs The TEQ equation is widely used for estimate risk of exposure cPAHs which can be calculated as (Eq. (1): (Yang et al., 2007; Yu et al., 2008; Jia et al., 2011; Vu et al., 2011; Sarkar and Khillare, 2012): TEQ = Σi[Ci x TEFi]

(1)

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were Ci is the concentration of an individual PAH and TEFi is the toxic equivalent factor. The development of the TEFs for PAHs can be used to characterize the carcinogenic properties of PAHs. Benzo(a)pyrene (BaP) was used as a reference compound. The cPAHs, which have lower potency than BaP, will be assigned to different TEF values.

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Three equations were calculated for TEQ based on Nisbet and Lagoy (1992) (Eq. (1.1), U.S. EPA (1993) (Eq. (1.2)), and Cecinato (1997) (Eq. (1.3)).

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In this formula the symbols for the chemicals denote their concentrations.

TEQ = 0.001 (Nap+ Acy+ Ace + Flu + Phe + Fla +Pyr)+ 0.0 (Ant + BPer +Chr) + 0.1(BaA + BbF + BkF + Ind)+ BaP + DbA

(1.1) (1.2)

TEQ= 0.01 (Chr)+ 0.1 (BaA + BbF+ BkF +Ind) + BaP+ DbA

(1.3)

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TEQ=0.06 (BaA) + 0.07(BbF + BkF) + BaP + 0.08 (Ind)+0.6(DbA)

The TEQ values calculated from various equations mentioned above were not much different. The average of the TEQ values in two sites (NA01, NA02) for each seasons were reported in Table 8. The average of the TEQ values in urban-traffic site NA02 (0.48-1.06) was higher than that of the

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urban-background site NA01(0.30-0.47). The main reason for this might be due to the higher PM10 concentrations present in this study. In particular, the BaPTEQ values in NA02 was higher during

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winter season than other seasons. The average of the TEQ values in the summer was greater than that expected, it can be explained with the proximity of the NA02 site to the Naples harbor and relative increase vessel traffic in this season. Table 8

The average concentrations of TEQ calculated from different equations in NA01 and NA02 in the different seasons. Urban - background site (NA01)

Urban - traffic site (NA02)

Autumn Winter Spring Summer Autumn Winter Spring Summer TEQ(1,1)

0.38

0.47

0.30

0.48

0.74

1.07

0.48

0.78

TEQ(1,2)

0.33

0.45

0.29

0.45

0.67

1.02

0.45

0.74

TEQ(1,3)

0.38

0.47

0.30

0.47

0.73

1.06

0.48

0.77

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ACCEPTED MANUSCRIPT The incremental lifetime cancer risk, ILCR, in humans can be determined by calculating the lifetime average daily dose (LADD) of PAHs according to the USEPA guidelines (USEPA 2013).

LADD = (Cs *IR *ET *EF * ED/BW * AT) *CF

(1.4) (1.5)

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ILCR = LADD *cancer slope factor (CSF)

Where LADD is the amount of intake per kilogram of body weight per day of a chemical suspected of having adverse health effects when absorbed into the body over a long period of time. Cs represents the average concentration of a particular PAH (ng m-3); IR is the intake rate (IRA=0.83 m3h-1 for adults and IRc=0.5 m3h-1 for children up to the age of six); ET is the exposure time (21 h

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day-1), EF is the exposure frequency (350 days year-1) and ED represents the exposure duration (EDA (adults)=70 years and EDC (children)=6 years); CF is the unit conversion factor (CF=10−6);

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BW is the average body weight (it was assumed that BWA=70 kg for adults and BWC=15 kg for children), and AT is the average timing, which was ATA=25,550 days (70×365) for adults and ATC=2190 days (6×365) for children (Bozek et al. 2009).

LADD and ILCR values of the measured PAHs for human adults and children were calculated and they will be reported later.

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Human health risk assessment was based on the assumption that adults and children may be exposed to PAHs from the ambient. In this study it is evaluated human expose risk to airborne PAHs through inhalation of PM10 and the conditions considered were reported in equations 1.4 and 1.5, like in other works. The estimated ILCR value is obtained for only PAHs and for all

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considered. The USEPA in 2005 proposed as acceptable levels of ILCR to 10-6 to 10-4. Table 9

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The average concentrations of monitored PAHs (mg m-3) for the assessed period time. CSF values, calculated values of LADDc and LADDA and the increase of probability that the number of tumorous disease exceeds the general average among adults (ILCRA) and among children (ILCRc) in NA01. PAH

Concentration*CF(mg m-3) CSF (mg-1 Kg day) LADDA(mg Kg-1day-1) LADDC (mg Kg-1day-1)

ILCRA

ILCRC

5.06E-07

0.61

3.35925E-08

9.44368E-08

2.049E-08 5.761E-08

5.92E-08

0.0061

4.47498E-08

1.25803E-07

2.73E-10

B(b+k)F

1.37E-07

0.061

8.94094E-08

2.51352E-07

5.454E-09 1.533E-08

BaP

2.37E-07

6.1

7.87025E-08

2.21252E-07

4801E-07

Ind

1.41E-07

0.61

2.66947E-08

7.50453E-08

1.628E-08 4.578E-07

DbA

1.87E-07

6.1

2.60835E-09

7.33272E-09

1.591E-08 4.473E-08

BaA Chr

15

7.674E-10 1.35E-06

ACCEPTED MANUSCRIPT Table 10 The average concentrations of monitored PAHs (mg m-3) for the assessed period time. CSF values, calculated values of LADDc and LADDA and the increase of probability that the number of tumorous disease exceeds the general average among adults (ILCRA) and among children (ILCRc) in NA02. PAH

Concentration*CF(mg m-3) CSF (mg-1 Kg day) LADDA(mg Kg-1day-1) LADDC (mg Kg-1day-1)

ILCRA

ILCRC

7.78E-07

0.61

5.6609E-08

1.50854E-07

3.273E-08 9.202E-08

Chr

6.85E-08

0.0061

8.05078E-08

2.26327E-07

4.911E-10 1.381E-09

B(b+k)F

3.17E-07

0.061

1.64476E-07

4.62383E-07

1.003E-08 2.821E-08

BaP

3.87E-07

6.1

1.49281E-07

4.19666E-07

9.106E-07

2.56E-06

Ind

2.25E-07

0.61

8.98379E-08

2.52556E-07

5.48E-08

1.541E-06

DbA

3.37E-07

6.1

5.96918E-10

1.67808E-09

3.641E-09 1.024E-09

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BaA

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In this study, ILCR to human adults and children residing in the sampling areas were lower than the acceptable levels (Table 9-10) and so the probabilistic health risk to humans was low health risk to

4. Possible sources of PM10-bound PAHs 4.1 Diagnostics Ratios (DRs)

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residents in Naples.

The diagnostic ratios (DRs) between some of the PAHs were considered as the “fingerprint” of an emission source (Khalili et al., 1995; Dickhut et al., 2000), because they presented the

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characteristics of the specific in based to the formation mechanisms. Major sources of PAHs, especially in large urban areas, are gasoline and diesel vehicles (Rogge et al., 1993). Other significant sources are coal and oil combustion as well as biomass combustion (EC, 2001; Finlayson-Pitts and Pitts,2000). Some DR and possible PAHs sources were reported in Table 11.

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The Ind/(Ind+BPer) ratio can be used to identify traffic sources. The value in the range from 0.350.70 indicates that the PAHs were emitted from diesel engines (Ravidra et al 2006, Kaur et al 2013).

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The BaA/(BaA+Chr) ratios in the range from 0.35-0.70 was also used for identifying the dominant source of PAHs at the roadside environment and in particular the origin can be associated to diesel engines, vehicle emissions and wood burning (Kaur et al 2013). The different ratio BaP/(BaP+Chr) can be associated to gasoline or diesel engine (Kaur et al 2013).

16

ACCEPTED MANUSCRIPT Table 11 Diagnostic ratios and possible PAHs sources PAH Ratio

Possible sources Source

Reference Yunker et al 2002 Unburned petroleum

<0.2 0.4 Ind/(Ind+BPer) 0.30-0.70

BaP/(BaP+Chr)

Kaur et al 2013

Diesel engine

0.56

Coal

0.62

Wood burning

0.53

Vehicle emission

0.73

Diesel engine

0.07-0.24

Coal combustion

0.49

Gasoline

0.73

Diesel engine

Ravidra et al 2008 Kaur et al 2013

Kaur et al 2013

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BaA/(BaA+Chr)

Gasoline

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Value

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In this study, some diagnostic ratios of the selected PAHs were calculated (Table 12) and compared with the references PAHs profiles (Table 11). Table 12

Diagnostic ratios during four seasons in NA01 and NA02 Urban - background site (NA01)

Urban – traffic site (NA02)

Autumn Winter Spring Summer Autumn Winter 0.38

0.41

BaA/(BaA+Chr)

0.56

0.73

BaP/(BaP+Chr)

0.48

0.67

0.28

0.50

0.33

0.37

0.33

0.39

0.50

0.59

0.52

0.70

0.51

0.50

0.80

0.64

0.50

0.70

0.67

0.71

TE D

Ind/(Ind+BPer)

Spring Summer

In NA01 and NA02, from data analysis reported in the Table 12, it is possible to highlight as the

EP

values obtained for all three considered DR: Ind/(Ind+BPer) (0.30-0.50), BaA/(BaA+Chr) (> 0.50), BaP/((BaP+Chr) (0.5-0.75), indicated that PAHs could be originated from engine emissions.

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Based on these ratio alone, it could not be concluded what is the major source of PAHs, but this ratio value suggested that the diesel engine source played a more important role than the gasoline source.

4.2 Principal components analysis (PCA) Principal component analysis (PCA) was used in this study to identify the main sources of PAHs pollution in the atmosphere and to determine the sources of PAHs (Jamhari et al 2013; Andrade et al 2009). The Factors for Varimax rotated components of the two observatory sites during different seasons were composed three components (Factor 1, Factor 2 and Factor 3) (Table 13). For NA01 Factor 1 (36.5% of the total variance) was highly loaded with high molecular weight PAHs (Ind, BPer) and Fla, which are associated with gasoline emission (Guo et al., 2003; Khalili et al.1995, 17

ACCEPTED MANUSCRIPT Masclet et al. 1986); Factor 2 (28.9% of the total variance) showed high loading of Chr, B(B+k)F which indicated diesel-powered emission (Khalili et al 1995); Factor 3 (34.6 % of the total variance) contained Phe, Pyr and BaP, that are suggested to have a common origin, that can be associated to traffic emission. In NA02 the Factor 1 (40.5 % of the total variance) showed high molecular weight (Ind and BPer).

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Ind and BPer can be associated to diesel emission (Li and Kamens,1993). The Factor 2 (31.4% of the total variance), contained BaA, B(b+k)F and it can be associated to gasoline and diesel emissions (Ravidra et al. 2008). The Factor 3 (28% of the total variance) contained BaP was indicative of a stationary emission point, that uses heavy oils as fuel (Yang et al 2002). PCA

Table 13

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showed that in the considered sites, the sources of PAHs were predominated from vehicle emission.

Comparison factor of PAHs-bound PM10 in NA01and in NA02

PAH

Factor 1

Factor 2

Phe Fla

Factor 3

Factor 1

Factor 2

Factor 3

0,896

0,744

Pyr

0,793

BaA 0,895

B(b+k)F

0,973

BaP

TE D

Chr

0,945 0,937

0,966

0,793

BPer

0,908

0,978 0,925 0,963

EP

Ind

5. Conclusions

Urban – traffic site (NA02)

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Urban - background site (NA01)

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The concentration of PAHs in PM10 determined at two sampling stations (NA01 and NA02) was dominated by higher molecular PAHs. In particular the sum of 5 and 6 ring PAHs, which are high molecular weight PAHs, was 50% of sum of PAHs detected at two sampling stations. The contribute of PAHs species such as B(b+k)F, BaP, Ind, BPer showed the originate from traffic emission. Principal component analysis (PCA) and diagnostic ratio also showed that the main sources of PAHs pollution in NA01 and NA02 were motor vehicle exhausts (gasoline and diesel engine emissions with some minor contributions from natural sources). The estimated incremental life time cancer risk (ILCR) from exposure to airborne TEQ is negligible. This suggests a low carcinogenic risk to population residing in these areas. Further comprehensive analysis using finer fraction of atmospheric aerosols, such as PM2.5 and PM1 is necessary. 18

ACCEPTED MANUSCRIPT Acknowledgements This work was supported by the “Assessorato all’Ambiente (Qualità della Vita) della Provincia di Napoli”. Paola Di Vaio gratefully acknowledges Provincia di Napoli for funding her PhD fellowship. Graphic location of sampling sites, Urban-background site (NA01) and Urban-traffic site (NA02) were provided by Ufficio Sistema Informativo Territoriale e Cartografia della Città

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Metropolitana di Napoli: the assistance of the staff has been gratefully appreciated.

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ACCEPTED MANUSCRIPT Yang, X., Okada, Y., Tang, N., Matsunaga, S., Tamura, K., Lin, J., Kameda, T.,Toriba, A., Hayakawa, K., 2007. Long-range transport of polycyclic aromatic hydrocarbons from China to Japan. Atmos. Environ. 41, 2710–2718. Yu, Y., Guo, H., Liu, Y., Huang, K., Wang, Z., Zhan, X., 2008. Mixed uncertainty analysis of polycyclic aromatic hydrocarbon inhalation and risk assessment in ambient air of Beijing. J.

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Environ. Sci. 20, 505–512. Wiriya, W., Prapamontol, T., Chantara, S., 2013. PM10 bound polycyclic aromatic hydrocarbons in Chiang Mai (Thailand): seasonal variations, source identification, health risk assessment and

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their relation-ship to air-mass movement. Atmos. Res. 124, 109-122.

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Highlights •

Concentrations of PM10 and PAHs were mean high during winter time in two sites.

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5 and 6 ring PAHs had a large contribute of total PAHs concentration in PM10.

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Diagnostic ratio analysis and PCA suggested a substantial contributions from traffic emission.

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Toxicity equivalent level based on PAHs revealed a low risk to residents in these areas.

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Graphical Abstract

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