Use of the PAH fingerprints for identifying pollution sources

Urban Climate xxx (2014) xxx–xxx

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Urban Climate journal homepage: www.elsevier.com/locate/uclim

Use of the PAH fingerprints for identifying pollution sources Angelo Cecinato ⇑, Ettore Guerriero, Catia Balducci, Valeria Muto Istituto sull’Inquinamento Atmosferico – CNR, I-00015 Monterotondo Scalo RM, Italy

a r t i c l e

i n f o

Article history: Received 24 May 2013 Revised 7 January 2014 Accepted 13 April 2014 Available online xxxx Keywords: Polynuclear aromatic hydrocarbons PAH Molecular markers Diagnostic (concentration) ratios Ambient pollution Source apportionment

a b s t r a c t Molecular signatures are investigated since long time for source assessment; characteristic behaviours are sought both in emission and aerosol composition. In this study, particulates released by stationary and vehicle sources were characterised for PAH contents by using similar top-to-bottom procedures. Group fingerprints and concentration ratios between pairs of compounds were investigated. The approach based on diagnostic ratios was applied to the study-cases of cities lying in Northern, Central and Southern Italy, and of localities in the Rome province, exposed to emission sources of different strength and nature. The results were compared with those observed in the Mediterranean Sea Region. In general, vehicles were confirmed as the principal source of PAHs, while minor and season dependent contributions could be associated to wood burning and soil resuspension. Original molecular signatures identified felt promising in the perspective of the PAH source reconciliation. Ó 2014 Elsevier Ltd. All rights reserved.

Compound symbols: PAH, polynuclear aromatic hydrocarbon; FP, fingerprint (molecular signature); DR, diagnostic concentration ratio; MW, molecular weight; AN, anthracene; BaA, benz[a]anhracene; BbF, benzo[b]fluoranthene; BjF, benzo[j]fluoranthene; BkF, benzo[k]fluoranthene; BFs, BbF+BjF+BkF; BghiF, benzo[ghi]fluoranthene; BPE, benzo[ghi]perylene; BeP, benzo[e]pyrene; BaP, benzo[a]pyrene; CH, chrysene; CP, cyclopentapyrene; DBA, dibenz[a,h]anthracene; DBaeP, dibenzo[a,e]pyrene; DBahP, ⇑ Corresponding author. Address: Istituto sull’Inquinamento Atmosferico – CNR, Via Salaria km 29.3 (P.O. Box 10), I-00015 Monterotondo Scalo RM, Italy. Tel.: +39 06 90672 260/273; fax: +39 06 90672 660. E-mail address: [email protected] (A. Cecinato). http://dx.doi.org/10.1016/j.uclim.2014.04.004 2212-0955/Ó 2014 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Cecinato, A., et al. Use of the PAH fingerprints for identifying pollution sources. Urban Climate (2014), http://dx.doi.org/10.1016/j.uclim.2014.04.004

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dibenzo[a,h]pyrene; DBaiP, dibenzo[a,i]pyrene; DBalP, dibenzo[a,l]pyrene; FA, fluoranthene; IP, indeno[1,2,3-cd]pyrene; PE, perylene; PH, phenanthrene; PY, pyrene; TR, triphenylene. tPAHs, sum of PAHs. Site symbols: BEL, Belloni (urban, residential); CYP, Cipro (urban, residential); FRA, Francia (urban, traffic); VAD, Villa Ada garden (urban backgroud); CFE, Colleferro town; CIA, Ciampino town; CIV, Civitavecchia town; CGU, Castel di Guido (rural, regional background); GUI, Guidonia town; MAG, Malagrotta (suburban); MLI, Montelibretti (semi-rural); TCA, Tenuta del Cavaliere (suburban).

1. Introduction Thousands of compounds are comprised in organic matter associated to airborne particles (Tsapakis et al., 2002; Pio et al., 2001; Guo et al., 2003; Bin Abas et al., 2004); many of them are mutagenic and carcinogenic (Graedel et al., 1986; Bayona et al., 1994). Special attention is paid to polynuclear aromatic hydrocarbons (PAHs) (Neilson, 1998; Pandey et al., 1999; Park et al., 2002; Callen et al., 2011). BaP is the only target compound in the legislation aimed at preserving air quality (European Commission, 2001; European Parliament and Council, 2008). Nevertheless, BaP is not the only PAH, nor the most potent one (MDH, 2013). Individual PAHs are not univocally associated to any source; the only important exception is retene, released by coniferous wood (Guenther et al., 1988; Freeman and Cattel, 1990). Thus, information about the nature of emission is drawn by investigating their relative amounts, and either PAH pairs (diagnostic ratios [DRs]) or groups (fingerprints [FPs]) are taken in account. Source reconciliation through PAH signature has been criticised (Marchand et al., 2004; Zhang et al., 2005), but the principal reasons of uncertainty have been elucidated; in particular, this approach remains reliable (Katsoyiannis and Breivik, 2014) provided reactivity, gas-to-particle partition, particle size distribution, meteorology, and water solubility are taken in account (Galarneau 2008; Kim et al., 2009; Dvorskà et al., 2012). Indeed, light PAHs (naphthalene to phenanthrene) are overall gaseous at ambient conditions; other compounds (e.g. fluoranthene) partition between gas and particle phases; only PAHs with molecular weights exceeding 252 atomic mass units, e.g., benzo[a]pyrene, are mostly associated to particulates (Coutant et al., 1988; Lu et al., 2008; Akyüz and Cabuk, 2010). PAHs display different reactivity in the atmosphere, though they decompose more easily when adsorbed on particle surface than trapped in its core, or associated to inorganic substrates than to carbonaceous matter (Masclet et al., 1986; Kim et al., 2009; Dvorskà et al., 2012). As a result, PAHs undergo the ageing process, which modifies the molecular signature in the interval between release and collection. A set of PAH DRs and FPs was identified for source reconciliation (Daisey et al., 1986; Sicre et al., 1987; Li and Kamens, 1993; Rogge et al., 1993a,b; Khalili et al., 1995; Gogou et al., 1996; Rogge et al., 1997, 1998; Kavouras et al., 1999; Schauer et al., 1996, 1999, 2002; Fraser et al., 2003; Manoli et al., 2004; Ravindra et al., 2008; Katsoyiannis et al., 2011; Tobiszewski and Namiesnik, 2012). Source apportionment based on PAH molecular signature was applied to sediments, soil and ice core (Kavouras et al., 1995; Fraser et al., 1999; Yang et al., 1998, 2002; Oanh et al., 1999; Mastral and Callén, 2000; Oda et al., 2001; Wornat et al., 2001; Fernandes and Brooks, 2003; De Abrantes et al., 2004; Lodovici et al., 2004; Ding et al., 2007). Table 1 lists the DRs usually adopted for this purpose. Attention was also paid to alkyl-PAHs, e.g. to methyl and dimethyl phenanthrenes, and to ratio between the unsubstituted compounds and total alkylated homologues (Boehm, 2006). Less frequent was the use of PH/AN, BbF/BkF, and light- vs. high-molecular weight PAHs ratios. Intrinsic limitations of this approach rely in the amount of indexes usually taken in account (four or less) and in the different DRs chosen by Authors. Besides, the PAH profiles discussed in technical literature are extrapolated to categories from individual emission sources, although these latter have distinctive features and run at particular conditions; moreover, differences exist among chemical analysis techniques applied. These reasons, combined with mechanisms modifying the PAH composition, explain why the emissions are characterised by ranges of DRs rather than by strict diagnostic values. Table 1 well depicts the utility and limits of the DR approach. For instance, the BaA/(BaA + CH) ratio usually exceeds 0.5 in all industrial emissions but is below 0.5 in vehicle and in domestic heating exhausts; the mean IP/(IP + BPE) ratio reaches 0.8, 0.4 and 0.55, respectively, in the emissions Please cite this article in press as: Cecinato, A., et al. Use of the PAH fingerprints for identifying pollution sources. Urban Climate (2014), http://dx.doi.org/10.1016/j.uclim.2014.04.004

Source (plant)

Location/matter

FA/ (FA + PY)

BaA/ (BaA + CH)

BaA/ (BaA + BaP)

Cement plant

Electro-static precipitator Stack emission filter Raw material (1) Quarry raw material Pyro-compressor Manufacturing (1) Manufacturing (2)

0.50

0.79

0.33

0.46 0.53 0.46 0.24 0.49 0.25

0.92 0.91 0.85 0.59 0.47 0.58

PY/BaP

BFs/ BPE

BaP/ BPE

IP/ (IP + BPE)

BaP/ (BaP + BeP)

0.54

25

1.43

0.43

0.46

0.21

a

0.67 0.68 0.70 0.12

0.57 0.62 0.67 0.09

46 79 12 1.12

2.25 1.67 1.80 13 1.68 7.8

3.0 2.7 1.40 1.51 1.17 17

0.94 0.96 0.94 0.65 0.94 0.65

0.08 0.09 0.15 0.41 0.13 0.75

a a a a a b

Asphalt production Vehicle production (1) Vehicle production (2) Electro-plating Lead smelter coke Bronze smelter Scrap metal incinerator Fertiliser production (1) Fertiliser production (2)

0.39 0.58

0.77 0.94

0.59 0.25

0.59 0.80

7.5 9.0

0.94 1.80

0.68 0.10

0.50 0.70

0.23 0.06

a a

0.48

0.85

0.17

0.69

6.5

1.48

0.08

0.60

0.15

a

0.54 0.60 0.32 0.56

0.77 0.81 0.79 0.94

0.29 0.74 0.61 0.96

0.61 0.80 0.71 0.90

4.0 3.2 127 20

0.98 1.07 1.23 1.64

0.18 1.25 0.92 2.57

0.61 0.36 0.69 0.51

0.23 0.19 0.21 0.06

a a a a

0.42

0.99

0.87

0.95

11

1.01

22

0.23

0.01

a

0.40

0.90

0.50

0.68

5.3

0.88

1.40

0.83

0.10

a

Steel

Plant (coke fuelled) (oil fuelled) (electricity powered) Coke oven Basic oxygen furnace Blast furnace Electric arc furnace

0.40 0.42 0.35 0.36 0.24 0.21 0.23 0.25

0.88 0.86 0.68 0.85 0.09 0.48 0.17 0.42

0.71 0.96 0.68 0.80 0.07 0.18 0.10 0.02

0.72 0.87 0.73 0.75 0.04 0.08 0.01 0.06

3.3 11 3.5 15 0.26 1.71 0.28 0.61

1.74 1.73 3.6 2.17 17 11 9.8 7.1

1.71 1.56 0.84 1.18 16 3.2 2.30 4.3

0.37 0.21 0.61 0.37 0.21 0.43 0.51 0.64

0.13 0.14 0.32 0.15 0.91 0.52 0.83 0.58

a c c c b b b b

Power produ.

Heavy oil fuelled Oil fuelled

0.24 0.21

0.12 0.39

0.02 0.09

0.03 0.15

0.28 1.69

8.6 5.5

291 10

0.35 0.31

0.88 0.61

b b

Paved roads

(1) (2)

0.52 0.61

0.69 0.33

0.50 0.11

0.71 0.33

5.0 0.94

2.48 2.00

0.06 0.02

0.61 0.91

0.31 0.67

a a

Industries

CH/ (CH + BaP)

Refs.

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Please cite this article in press as: Cecinato, A., et al. Use of the PAH fingerprints for identifying pollution sources. Urban Climate (2014), http://dx.doi.org/10.1016/j.uclim.2014.04.004

Table 1 PAH DR adopted in scientific literature for emission characterization/source identification.

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Source (plant)

Location/matter

FA/ (FA + PY)

BaA/ (BaA + CH)

BaA/ (BaA + BaP)

Soil

Dust (1) Dust (2)

0.42 0.52

0.81 0.84

0.81 0.59

Street dust

Soil (1)

0.50

0.35

0.58

Soil (2) Paved

0.56 0.41

0.24 0.45

0.58 0.40

Oil fuelled (1) Oil fuelled (2) Coal fuelled Oak wood fuelled (1) Oak wood fuelled (2) Pine wood fuelled (1) Pine wood fuelled (1) Synthetic log fuelled Mixed wood

0.67 0.62 0.55 0.55 0.43 0.59 0.44 0.43

0.30 0.68 0.44 0.40 0.07 0.50 0.39 0.34 0.43

0.66 0.36 0.71 0.43 0.48 0.09 0.50 0.49 0.55

Heavy-duty diesel Light-duty diesel* Light-duty diesel** Non catalysed car (1) Non catalysed car (2) Catalysed car (1) Catalysed car (2) Catalysed car (3) Catalysed car (4)

0.38 0.37 0.60 0.35 0.61 0.14 0.44 0.38 0.40–0.60

0.73 0.29 0.49 0.58 0.57 0.76 0.33

0.47 0.50 0.47–0.63 0.83 0.63 0.80 0.50

House heating

Vehicles

0.38–0.50

CH/ (CH + BaP) 0.68 0.71

PY/BaP

BFs/ BPE

BaP/ BPE

IP/ (IP + BPE)

BaP/ (BaP + BeP)

13 5–10

1.26 1.0– 2.4

0.11 <0.16

0.51 0.54

0.19 0.1–0.2

1.3– 4.7 2.23 1.45

1.07

0.37

0.47

d; e; f; g; h

0.85 0.45

0.75 0.53

0.52 0.17

a a

0.67 0.32 0.50 0.56 0.64 0.75 0.67 0.48 0.66

i a i i j i j j k; l; m; f; n

0.36 0.57 0.30 0.13 0.49 0.19 0.49

a e; i; k; m f; d; l; t; u; v; w; g a d a d o; p e; f; q; r; s

0.82 0.54 0.76 0.53 0.92 0.09 0.61 0.65

9.2 8.2 5.4 2.78 2.30 0.25 2.56 2.35

0.08 2.68 0.10 0.07 4.5 0.09 4.1 2.06 2.18

0.01 109 0.03 0.04 1.77 0.15 1.94 0.77

0.25 0.71 0.50 0.78 0.56 0.56 0.67 <0.65 0.30

3.1 6.7

0.15 1.42 1.60 1.17 0.58 0.45 1.16

0.35

46 0.71 25 1.32 0.80– 1.22

0.59 0.58 0.30 0.33 0.40

0.82

0.54 0.52 0.33 0.59 0.50 0.45 0.51 0.18 0.26 0.27 0.27 0.24–0.32

Refs.

a a

Rem.: for the gasoline and motorbike emissions, digits refer to condensable exhausts collected at the muffler/catalytic converter ends. References: (a) Manoli et al. (2004); (b) Yang et al. (1998); (c) Yang et al. (2002); (d) Rogge et al. (1993b); (e) Boonyatumanond et al. (2007); (f) Li and Kamens (1993); (g) Oda et al. (2001); (h) Fernandes and Brooks (2003); (i) Ravindra et al. (2008); (j) Rogge et al. (1998); (k) Ravindra et al. (2006); (l) Katsoyiannis et al. (2011); (m) Kavouras et al. (2001); (n) Gogou et al., 1996; (o) Pio et al. (2001); (p) Akyüz and Cabuk (2010); (q) Tsapakis et al. (2002); (r) Masclet et al. (1986); (s) Guo et al. (2003); (t) Pandey et al. (1999); (u) Park et al. (2002); (v) Khalili et al. (1995); (w) Sicre et al. (1987). * Particulates only. ** Vapour + particulates.

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Table 1 (continued)

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released by cement, steel and mixed industrial plants, 0.5 in diesel particulates and 0.25 in gasoline-fuelled car exhausts; different DRs have been calculated for oak and pine wood combustion by Rogge et al. (1998), and Ravindra et al. (2008). Multiple regression or principal component analysis, used today for source reconciliation, include the PAH profiles within a list of chemical indexes (elemental and organic carbon, inorganic anions and metals) (Simoneit, 1984; Kavouras et al., 2001; Li et al., 2003; Braga Dallarosa et al., 2005; Larsen, 2008; Sofowote et al., 2010; Brown and Brown, 2012). The emission FPs were probably identified first, but DPs are often used. The FP model seems to fit better with the whole emission and all airborne PAHs, whose profile is obtained by collecting also the lighter and more volatile substances; by contrast, DPs depict the PAH behaviours typical of sources with a few indexes (Hanedar et al., 2011; Jang et al., 2013; Khairy and Lohmann, 2013). In our study, PAHs released by several stationary and mobile sources were determined and the respective fingerprints were identified. Industrial fumes, power and heating plant emissions, vehicle exhausts and waste treatment residues were investigated. Diagnostic ratios were applied to infer the airborne PAH sources in Italy; the results were compared to those observed in Mediterranean Sea Region cities. 2. Experimental 2.1. Particulate sampling and analysis Self-combustion particulates (PM10) of urban wastes were collected at medium-volume conditions (1 m3 h 1) inside an open-sky landfill; sixteen samples were collected and gathered seasonally. Soap industry exhausts were collected with the same procedure inside the manufacturing plant area. Leaves and branches of mixed vegetation were burnt in open air and the fumes were aspired (5 L min 1, 15 min) onto quartz fibre filters, 2 m away from fires; two pairs of samples were collected at flaming and smouldering conditions. Industrial emissions were sampled at stacks according to technical normative, using quartz cartridges (Mosca et al., 2010); usually four samples per manufacturing type were analysed. As for vehicles, dusts were recovered from gasoline fuelled cars and motorbikes by scraping mufflers; light-duty diesel exhausts were sampled onto quartz filters at a roller-bench, after dilution with ultra-pure air, while urban cycle was simulated (Mabilia et al., 2003). Up to eight dusts per category of vehicle mileages were collected. Cigarette side-stream smokes were sampled at low volume conditions (6 L min 1) in a dedicated room. PAHs were determined in all cases by applying a consolidated procedure (Di Filippo et al., 2005). Briefly, PAHs were extracted with pressurised solvent mixture (toluene/methanol) and fractionated by elution on neutral alumina. PAHs were recovered with dichloromethane and processed through capillary GC-MSD (EI-SIM), using perdeuterated homologues as reference compounds; the column was DB5-MS. Analytical uncertainty never exceeded 16% (Borsella et al., 2004). 2.2. Selection of PAH fingerprints and diagnostic ratios in emissions The relative PAH contents in the emissions were depicted in two ways. First, the diagnostic ratios adopted by technical literature were calculated in our samples. Second, the molecular fingerprints were drawn by normalising the emission factors or neat concentrations of all PAHs vs. indeno[1,2,3-cd]pyrene (IP). The two approaches provided different looks of the organic particulate composition, the FP model displaying an overview of the PAH signatures, and DPs focusing the concern on a handful of substances. Nine diagnostic ratios were selected in total, under the following criteria: (i) all DR formulas included PAHs of similar or low vapour pressures, to minimize the uncertainty induced by volatilisation (thus, PAHs up to phenanthrene were neglected); and (ii) compounds easily decomposing in ambient air were not examined, due to small amounts recorded in airborne particulates compared to exhausts composition (Coutant et al., 1988). It is noteworthy that benzo[e]pyrene (BeP) was proposed elsewhere as the reference compound for PAHs (Daisey et al., 1986). Nevertheless, BeP was often omitted in emission analyses, due to low toxicity; thus, the literature data archives were insufficient to normalise individual PAHs vs. this Please cite this article in press as: Cecinato, A., et al. Use of the PAH fingerprints for identifying pollution sources. Urban Climate (2014), http://dx.doi.org/10.1016/j.uclim.2014.04.004

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compound. The degradation of reactive substances did not recommend the use of total PAHs for normalisation. 2.3. PAH monitoring in airborne particulates The PAH signatures were applied to estimate the emission impact, by calculating DRs in airborne particulates. Two in-field experiments were made. First, four cities (i.e. Milan, Florence, Rome and Naples) were investigated across Northern, Central and Southern Italy; samples were collected in residential districts. Second, twelve sites were investigated in Rome, namely: (i) in the city centre, the Villa Ada, Francia, Cipro and Belloni stations of Regional Air Pollution Network (ARPA Lazio Agency), representative of urban background, heavy traffic and residential areas, respectively; (ii) in the outskirts, the semi-rural zones of Malagrotta, hosting the city hospital waste incinerator, a big landfill and a refinery, and Tenuta del Cavaliere; and (iii) in the province, the towns of Ciampino, Civitavecchia, Guidonia (residential areas) and Colleferro (heavily influenced by industrial plants), Montelibretti (semi-rural) and Castel di Guido (rural, regional background). PAH monitoring campaigns were conducted in 2010–2011, during winter and summer; each experiment lasted two or three weeks. PM10 was collected daily onto quartz filters according to European normative (UNI-EN 12341 and UNI-EN 15549A methods), then weekly pools were gathered and processed through solvent extraction, column chromatography and GC-MSD analysis (Cecinato et al., 2010). 3. Results and discussion 3.1. PAH fingerprints and diagnostic ratios Table 2 provides the PAH percentages normalised vs. IP in our emissions samples. Compounds ranging from phenanthrene (MW = 178) to dibenzopyrenes (MW = 302) were investigated. As expected, the sources had different PAH profiles. For instance, the contributions of light compounds (up to pyrene) to the sum of PAHs (tPAHs) were very different between: (i) incineration wastes and urban refuses; (ii) cement and steel plant emissions; and (iii) exhausts released by power and heat generators. IP accounted for <1% of tPAHs in cement and power plant emissions, in waste incinerator exhausts and cigarette smoke, whilst its percentages reached 2–5% in urban refuse and biomass burning fumes as well as in steel plant emissions; by contrast, it exceeded 15% in the boiler exhausts. BaP was negligible in the fumes released by expanded clay and coal-fuelled cement manufacturing, and by oil/water emulsion fuelled power plant; on the other hand, it occurred at high percentages in the mixed-fuel cement manufacturing and oil-fuelled power plant exhausts, in tobacco smokes and biomass burning fumes. BaP was released at important extents by hospital and urban refuse incinerators, whilst it was not associated to cemetery and landfill smokes. Finally, the relative abundances of dibenzopyrenes varied with sources. The imperfect separation of benzofluoranthenes (BbF, BjF and BkF) induced an important loss of information (Poster et al., 2006). Despite different carcinogenic potencies were associated to BbF, BjF and BkF (MDH, 2013), BbF was not distinguished from BjF, or BjF from BkF, since the full characterization of isomers could be reached only combining different GC columns or different wave lengths in HPLC-FD (Knauer, 2013). Anyway, an important variability of the three BF percentages has been observed in the air of Rome, both indoors and outdoors (Fig. 1), thanks to use of new GC columns capable of separating also the benzanthracene/triphenylene/chrysene isomers (J&W DB-EUPAH, purchased from Agilent, Cernusco MI, Italy). That was indicative of emission fingerprints worth of further investigation. Moreover, PAHs with MWs equal to 226–228, 252, 276–278 and 300–302 had different percentage distributions in vehicle exhausts (Fig. 2), suggesting to include these subgroups in future studies. In particular, light-duty diesel particulates showed relative abundances of benzo[ghi] fluoranthene/cyclopentapyrene, benzofluoranthenes and coronene, well distinct from those typical of gasoline fuelled car and motorbike exhausts. Our PAH diagnostic ratios (Table 3) did not fit perfectly with technical literature (Table 1); important exceptions were observed, although in general the results were coherent. For instance with Please cite this article in press as: Cecinato, A., et al. Use of the PAH fingerprints for identifying pollution sources. Urban Climate (2014), http://dx.doi.org/10.1016/j.uclim.2014.04.004

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Table 2 PAH fingerprints, expressed as relative contents normalised vs. indeno[1,2,3-cd]pyrene, identified by us in exhausts. Stationary and diffuse emission sources. Manu. plant (fuel)

Expanded Cement Cement clay (oil) (coal) (coal/15% oil)

Cement (coal/ emulsion)

Cement (coal/ polymers)

Steel Power Power (oil, Power cokery (coal) 3% sulphur) (oil/ water)

Heat boiler (oil)

Soap

PH AN FA PY BaA CH + TR BbjF BkF BaP IP DBA BPE DBalP DBaeP DBaiP DBahP tPAHs BeP

384 13 28 11 1.7 3.2 3.4 1.11 0.08 1.00 0.26 0.55 0.26 0.32 0.35 0.00 448

52 24 16 9.0 1.27 2.8 1.09 0.62 0.60 1.00 1.09 1.74 0.70 0.87 0.00 0.00 113

188 7.5 72 35 0.86 0.93 1.67 1.05 1.40 1.00 0.14 0.54 0.91 0.81 0.32 0.23 312

1.39 0.25 3.70 1.78 1.68 1.71 2.1 0.79 1.35 1.00 0.27 0.82 0.00 0.03 0.14 0.10 17 1.06

0.20 0.03 0.48 0.58 0.58 0.57 0.98 0.25 0.51 1.00 0.27 0.62 0.18 0.00 0.03 0.01 6.0 0.36

7.9 0.29 4.3 3.8 0.82 2.19 1.10 0.81 0.57 1.00 0.07 1.55 0.13 0.03 0.07 0.00 25 0.97

35 3.0 8.7 4.3 0.43 0.40 0.11 0.17 0.06 1.00 0.31

54 22 12 16 0.87 0.89 8.2 4.2 5.1 1.00 3.4

0.00 0.00 0.00 0.00 53

0.00 0.00 0.00 0.00 128

19 18 8 10 0.55 0.4 0.72 0.37 0.64 1.00 5.0 0.37 0.00 0.05 0.27 0.16 65

100 136 20 40 1.00 2.0 3.0 0.33 6.0 1.00 8.0 1.00 0.00 1.00 0.00 0.00 320

129 104 33 48 0.68 3.4 4.1 0.00 0.00 1.00 7.8 0.68 2.57 0.32 2.25 0.00 337

Manu. plant (fuel)

urban urban waste waste refuses, incenerator, incenerator, refuses, incenerator landfill cemetery hospital

sewage sludge, fluid bed

biomass biomass tobacco sewage burning,pine burning, sludge,rotary smoking, straw sidestream wood kiln

PH AN FA PY BaA CH+TR BbjF BkF BaP IP DBA BPE DBalP DBaeP DBaiP DBahP tPAHs

96 28 77 60 13 16 6.3 2.55 1.28 1.00 0.19 1.78 0.00 0.82 0.00 0.00 303

23 6.3 7.0 2.0 0.33 0.38 1.57 4.7 0.62 1.00 2.22 1.05 1.68 3.6 5.5 1.58 63

10 2.1 1.5 2.9 0.60 0.33 1.42 1.09 0.80 1.00 2.21 0.98 0.27 0.64 0.53 0.03 26

207 76 553 90 113 57 15 6.4 0.00 1.00 0.00 1.49 0.00 0.00 0.00 0.00 1120

10 0.10 20 1.2 5.5 7.7 9.6 0.66 0.10 1.00 0.40 1.08 0.54 0.25 0.10 0.00 58

3.3 0.21 2.7 2.1 1.14 1.35 1.70 0.47 0.93 1.00 0.49 1.32 0.23 0.92 0.09 0.00 18

88 21 19 13 4.7 10 2.55 0.63 2.21 1.00 0.37 1.02 0.00 0.00 0.00 0.00 164

11 2.5 5.5 4.7 2.6 4.0 2.5 0.67 1.69 1.00 0.26 1.07 0.44 0.27 0.14 0.00 38

4.3 2.2 5.9 4.9 2.5 2.7 2.6 0.67 1.75 1.00 0.60 0.78 0.00 0.00 0.00 0.00 30

regards to BaA/(BaA + CH), light-duty diesels showed similar values in the two Tables (0.39) while gasoline-fuelled cars were characterised by higher ratios (>0.45); besides, the values reported for cement manufacturing emissions were quite different (0.70 vs. 0.40 in Tables 1 and 3, respectively), but similar in the case of oil-fuelled power plants (0.25 on the average). About the IP/ (IP + BPE) ratio, in the two tables similar values (0.9) were associated to cement plant emissions only if the exhausts of emulsion- and polymer blended fuels were cut off; light-duty diesel dusts showed higher values than gasoline-fuelled cars; and power plants were characterised by ratios equal to ca. 0.33 or 0.6, respectively, in Tables 1 and 3. 3.2. Atmospheric concentrations of PAHs and seasonal variability of molecular signatures Six PAH DRs were selected within the nine investigated; they were FA/(FA + PY), BaA/(BaA + CH), IP/(IP + BPE), CH/(BaP + CH); BaP/BPE and BaP/(BaP + BeP). The DR rates in the city aerosols are shown Please cite this article in press as: Cecinato, A., et al. Use of the PAH fingerprints for identifying pollution sources. Urban Climate (2014), http://dx.doi.org/10.1016/j.uclim.2014.04.004

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A. Cecinato et al. / Urban Climate xxx (2014) xxx–xxx

Fig. 1. Percentages of benzofluoranthene isomers observed in airborne particulates of Rome, depending on site and season time. (A) Schools; (B) office; (C) homes; (D) ARPA Lazio stations. Symbols: BbF, benzo[b]fluoranthene; BjF, benzo[j]fluoranthene; BkF, benzo[k]fluoranthene; wi., winter; sp., spring; su., summer; out, outdoor; in, indoor.

Fig. 2. Percentages of congeners belonging to 226–228, 252, 276–278 and 302 molecular weight PAH subgroups occurring in vehicle exhausts. Symbols: BghiF, benzo[ghi]fluoranthene; CP, cyclopentapyrene; BaA, benz[a]anthracene; CH, chrysene + triphenylene; BbjF, benzo[b]fluoranthene + benzo[j]fluoranthene; BkF, benzo[k]fluoranthene; BaF, Benzo[a]fluoranthene; BeP, benzo[e]pyrene; BaP, benzo[a]pyrene; PE, perylene; IF, indenofluoranthene; IP, indeno[1,2,3-cd]pyrene; BPE, benzo[ghi] perylene; DBahA, dibenz[a,h]anthracene; CO, coronene; DBahP, dibenzo(a,h)pyrene; DBaiP, dibenzo(a,i)pyrene; DBaeP, dibenzo(a,e)pyrene; DBalP, dibenzo(a,l)pyrene. LDD, light-duty diesels; MBK, motorbikes; GFC, gasoline fuelled cars.

in Fig. 3. The phenanthrene-vs.-anthracene ratio was cut, since both compounds are gaseous at P90% (Gundel et al., 1995; Tobiszewski and Namiesnik, 2012). The PY/BaP ratio was higher in summer (2.6–60) than in winter (0.5–1.0), although the opposite behaviour would be observed according to Please cite this article in press as: Cecinato, A., et al. Use of the PAH fingerprints for identifying pollution sources. Urban Climate (2014), http://dx.doi.org/10.1016/j.uclim.2014.04.004

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A. Cecinato et al. / Urban Climate xxx (2014) xxx–xxx Table 3 Typical PAH diagnostic ratios observed by us in emission particulates. A. Stationary/area sources; B. Motor vehicles.

(A) Manu. plants (fuel) Expanded clay (oil) Cement (coal) Cement (coal/15% oil) Cement (coal/ emulsion) Cement (coal/ polymers) Steel cokery Power (coal) Power (oil, 3% sulphur) Power (oil/water) Heat boiler (oil) Soap Waste incenerator, hospital Waste incenerator, cemetery Urban refuses incenerator Urban refuses landfill Sewage sludge, fluid bed Sewage sludge, rotary kiln Tobacco smoking, sidestream Biomass burning, pine wood Biomass burning, straw (B) Vehicles Light-duty diesels Motorbikes Gasoline fuelled cars

FA/ BaA/ (FA + PY) (BaA + CH)

BaA/ (BaA + BaP)

CH/ PY/BaP (CH + BaP)

BFs/ BPE

BaP/ BPE

IP/ BaP/ (IP + BPE) (BaP + BeP)

0.73 0.67 0.44 0.64

0.35 0.52 0.50 0.31

0.96 0.9 0.15 0.68

0.98 0.87 0.15 0.82

134 72 3.1 15

8.3

0.14

0.98 0.35

0.65 1.00 1.00 0.36

0.68

0.48

0.38

0.40

25

5.1

2.62

0.65

0.68 0.43 0.34 0.40 0.45 0.53 0.56

0.49 0.57 0.33 0.17 0.50 0.27 0.45

0.55 0.46 0.14 0.31 0.54 0.55–0.64 0.91

0.56 0.39 0.25 0.69 0.53 0.79 0.92

1.31 16 6.6 32 1.15 4.3–10 47

3.5 2.9 3.3 6.0 1.98 1.23 5.0

1.64 1.71 6.0 2.21 0.81 0.36 0.72

0.55 0.73 0.50 0.60 0.62 0.39 0.36

0.86

0.66

0.99

0.98

90

0.67

0.40

0.56

0.46

0.55

0.59

2.28

1.63 0.70

0.43

0.78 0.34

0.47 0.64

0.35 0.43

0.38 0.29

3.2 3.6

6.0 0.59 2.57 0.82

0.49 0.51

0.95

0.41

0.98

0.99

9.4

0.10

0.48

0.59

0.31

0.68

0.82

5.9

3.1

2.17

0.50

0.50

0.54

0.39

0.60

0.70

2.8

3.0

1.58

0.48

0.56

0.55

0.48

0.58

0.60

2.8

4.1

2.24

0.56

0.61

0.52 0.45 0.49

0.39 0.44 0.48

0.84 0.51 0.44

0.89 0.56 0.47

3.4 0.60 0.14

2.49 0.33 1.04 0.46 0.66 0.33

0.39 0.27 0.27

0.29 0.48 0.43

11

15

0.56

0.59 0.37

0.53

Rem.: for the gasoline and motorbike emissions, digits refer to condensable exhausts collected at the muffler/catalytic converter ends.

respective vapour pressures (Possanzini et al., 2006). This suggests the impact of seasonal emissions (e.g. domestic heating) and meteorology; in fact both frequent rains and low boundary layer heights, typical of winter in Italy, favoured the removal of coarse particles, relatively rich of light PAHs (Galarneau, 2008; Martellini et al., 2012). According to average DR rates [Table 3, BaA/(BaA + CH), BaA/(BaA + BaP) and BaP/(BaP + BeP) ratios], traffic was the principal source of PAHs in the four cities, influencing winter and summer fingerprints; gasoline and diesel vehicles were both important. Other sources were soil resuspension [see FA/(FA + PY) and IP/(IP + BPE) values], and house heating in winter [BaP/BPE, IP/(IP + BPE)]. At this regard, wood combustion was detectable in urban contexts, unlike what observed in previous investigations. Soil resuspension was noteworthy in Milan during summer, when high rates of BaA/ (BaA + CH) and BaA/(BaA + BaP) were found (i.e., 0.3 and 0.6, respectively). Similar results were obtained in Thessaloniki, Greece (Manoli et al., 2004). As for Milan, the new PAH signatures were compared with those observed in 2001 (Cecinato et al., 2003). Some DRs were unaltered [i.e., BaA/ (BaA + CH), BaA/(BaA + BaP), BaP/(BaP + BeP)], whilst wide variations characterised the others [e.g., in 2001 BaP/BPE reached 1.76 ± 0.19 in winter and 0.12 ± 0.01 in summer, and IP/(IP + BPE) was equal to 0.40 ± 0.02 in winter and 0.28 ± 0.01 in summer], which suggests the use of oil for domestic heating Please cite this article in press as: Cecinato, A., et al. Use of the PAH fingerprints for identifying pollution sources. Urban Climate (2014), http://dx.doi.org/10.1016/j.uclim.2014.04.004

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Fig. 3. PAH diagnostic ratios in airborne particulates of Italian cities during winter 2010–11. Symbols: as in Table 2.

and the impact of industries during winter. In winter, aerosols in Naples were characterised by the minimum DR values among the four cities (Fig. 3); by contrast in summer two ratios were low [i.e., BaA/(BaA + BaP) and BaP/BPE] and two were high [FA/(FA + PY) and IP/(IP + BPE)]. This finding was in accordance to previous studies (Caricchia et al., 1999), where gasoline vehicles were identified as the main PAH source in Naples. In Florence, Martellini et al. (2012) investigated PAHs in 2010; one site confirmed the importance of vehicle exhausts whilst a second, urban background, was mainly influenced by emission from soil. Also in Florence light PAHs were relatively abundant in summer, supporting the occurrence of seasonal sources. The BaP/(BaP + BeP) ratio reached 0.5 in winter and 0.3 in summer in all cities; apart from the impact of domestic heating, probably some BaP degradation occurred due to light and oxidants (Coutant et al., 1988; Kim et al., 2009). The PAH diagnostic ratios typical of Rome province are reported in Table 4. In winter, only small differences were observed between the average FA/(FA + PY), BaA/(BaA + CH), BaA/(BaA + BaP) and BaP/(BaP + BeP) rates calculated in downtown and in the countryside (Table 4A). Wider differences were found comparing the BaP/(BaP + BPE) ratios (0.59 ± 0.22 in the city and 0.94 ± 0.31 elsewhere), while the IP/(IP + BPE) ratio was equal to 0.46 ± 0.03 in downtown and 0.53 ± 0.01 in the countryside if the value of Civitavecchia was cut off. This suggest that diesel vehicles impacted more in the countryside than in the city. Civitavecchia was often characterised by the lowest DR values (Table 4). Thus, this site was probably influenced by quite aged emissions (Katsoyiannis and Breivik, 2014), since the source mix was roughly that of all other localities from the Rome countryside. The DR rates in summer were lower than in winter, except for BaA/(BaA + BaP) in downtown (Table 4). This finding, combined with the concurrent low FA/(FA + PY) ratio, seemed to suggest the occurrence of an another source. In conclusion, the PAH patterns put in the evidence light-duty vehicles, incinerators and wood burning as PAH sources, besides dust resuspension in summer. Looking to other Mediterranean Region cities, diesel vehicles were primary PAH sources in Zaragoza and in Alexandria, Egypt, (Callén et al., 2011; Khairy and Lohmann, 2013). Vehicle traffic was predominant also in Greater Athens (Mantis et al., 2005), despite minor contributions came out from industrial furnaces, in Madrid (Mirante et al., 2013), where the contribution of heating (coal) could Please cite this article in press as: Cecinato, A., et al. Use of the PAH fingerprints for identifying pollution sources. Urban Climate (2014), http://dx.doi.org/10.1016/j.uclim.2014.04.004

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A. Cecinato et al. / Urban Climate xxx (2014) xxx–xxx Table 4 PAH diagnostic ratios in airborne particulates of Rome and its province in winter and summer. FA/(FA + PY)

BaA/(BaA + CH)

BaA/(BaA + BaP)

BaP/BPE

IP/(IP + BPE)

BaP/(BaP + BeP)

(A) Winter BEL I BEL II CYP I CYP II FRA I FRA II VAD I VAD II Rome centre TCA I TCA II MAG I MAG II CGU I CGU II CIA I CIA II CFE I CFE II GUI I GUI II CIV I CIV II MLI I MLI II Rome province

0.59 0.59 0.58 0.59 0.57 0.57 0.61 0.60 0.59 ± 0.02 0.62 0.61 0.62 0.63 0.66 0.64 0.63 0.60 0.60 0.62 0.61 0.60 0.60 0.65 0.60 0.59 0.62 ± 0.02

0.34 0.33 0.30 0.30 0.34 0.34 0.27 0.27 0.31 ± 0.03 0.38 0.36 0.35 0.37 0.26 0.22 0.36 0.36 0.34 0.33 0.32 0.26 0.28 0.20 0.27 0.28 0.31 ± 0.06

0.43 0.41 0.40 0.40 0.42 0.42 0.34 0.36 0.40 ± 0.03 0.45 0.45 0.47 0.49 0.37 0.33 0.50 0.48 0.47 0.49 0.41 0.44 0.41 0.36 0.21 0.35 0.43 ± 0.08

0.96 0.91 0.41 0.40 0.52 0.46 0.58 0.47 0.59 ± 0.22 1.26 1.12 1.02 1.03 0.91 0.85 1.06 1.05 1.31 1.41 1.12 0.99 0.49 0.29 0.57 0.60 0.94 ± 0.31

0.50 0.50 0.42 0.42 0.44 0.44 0.47 0.46 0.46 ± 0.03 0.54 0.55 0.53 0.53 0.54 0.54 0.53 0.53 0.53 0.52 0.51 0.52 0.43 0.35 0.50 0.51 0.51 ± 0.05

0.52 0.51 0.41 0.41 0.45 0.45 0.44 0.41 0.45 ± 0.04 0.56 0.55 0.53 0.54 0.49 0.47 0.54 0.54 0.55 0.54 0.52 0.50 0.37 0.20 0.47 0.45 0.49 ± 0.09

(B) Summer BEL I BEL II CYP I CYP II FRA I FRA II VAD I VAD II Rome centre TCA I TCA II MAG I MAG II MLI I MLI II Rome province

0.36 0.39 0.34 0.39 0.36 0.29 0.36 0.27 0.35 ± 0.04 0.44 0.40 0.29 0.32 0.33 0.27 0.34 ± 0.06

0.26 0.28 0.13 0.28 0.36 0.29 0.25 0.25 0.26 ± 0.06 0.29 0.27 0.21 0.17 0.20 0.17 0.22 ± 0.05

0.43 0.46 0.63 0.55 0.75 0.78 0.48 0.47 0.57 ± 0.14 0.49 0.42 0.43 0.44 0.33 0.33 0.41 ± 0.06

0.63 0.71 0.48 0.55 0.62 0.51 0.67 0.57 0.59 ± 0.08 0.71 0.76 0.94 0.51 1.03 0.71 0.78 ± 0.19

0.46 0.51 0.28 0.42 0.29 0.53 0.44 0.42 0.42 ± 0.09 0.52 0.51 0.47 0.46 0.41 0.42 0.46 ± 0.05

0.44 0.39 0.26 0.38 0.31 0.23 0.40 0.38 0.35 ± 0.07 0.44 0.45 0.46 0.28 0.46 0.40 0.41 ± 0.07

Italic characters have been used to distinguish the DR means for Rome and its Province from values caalculated at each site.

not be neglected in winter, in Bursa, Turkey (Esen et al., 2008), and in Algiers (Ladji et al., 2009). In Thessaloniki, Greece, mobile sources (with variable contributions of gasoline and diesels vehicles) were the most important ones in both seasons, although metal industry and oil burning exhausts could contribute to airborne PAHs (Manoli et al., 2004). PAH profiles similar to Naples were found in downtown Algiers and Istanbul (Yassaa et al., 2001; Hanedar et al., 2011), where the relative importance of vehicle types changed with the sampling site. Menichini et al. (1999) also highlighted the importance of traffic, monitoring PAHs in Rome over a decade. In conclusion, vehicles were identified as the major PAH source over the Mediterranean Sea Region. Nevertheless, wood burning and soil dust resuspension seemed to gain concern, probably owing to the renewing the vehicular fleet and the adoption of renewable energy policies.

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A. Cecinato et al. / Urban Climate xxx (2014) xxx–xxx

4. Conclusions Information about the pollution sources in Italy could be drawn from the molecular signature of PAHs in airborne particulates after an extensive study of known and original diagnostic ratios was performed. Vehicles were confirmed as the major pollution source, in accordance to other Mediterranean Region cities. Nevertheless, wood burning and soil resuspension will gain concern in the future, whilst industrial emissions and oil exhausts in heating plants will lose importance. The ageing of emission could be recognised at one of the sites. According to fingerprints observed in emission and airborne particulates, molecular signatures including PAHs other than the sixteen priority compounds will provide further insights to reconcile sources of air pollution. 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