Extended Technical Report on Indoor/Outdoor monitoring of PAHs, PM2.5 and its chemical components with ancillary measurements of gaseous toxicants in the

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Extended Technical Report on Indoor/Outdoor monitoring of PAHs, PM2.5 and its chemical components with ancillary measurements of gaseous toxicants in the

frame of the EXPAH Project (Action 3.3)

A. Cecinato, P. Romagnoli, C. Balducci, E. Guerriero, M. Perilli, F. Vichi, A. Imperiali, C. Perrino, L. Tofful, T. Sargolini, M. Catrambone, S. Dalla Torre, E. Rantica CNR, Istituto sull’Inquinamento Atmosferico, Monterotondo Stazione, Roma;

cecinato@iia.cnr.it, perrino@iia.cnr.it

M. Gherardi, M.P. Gatto, A. Gordiani, N. L‟Episcopo, C. Gariazzo

INAIL, Settore Ricerca, Dipartimenti Igiene del Lavoro e Installazioni di Produzione e Insediamenti Antropici

Monte Porzio Catone, Roma; m.gherardi@inail.it

F. Sacco, R. Sozzi, F. Troiano, F. Barbini, C. Gargaruti, A. Bolignano ARPALazio

fabrizio.sacco@arpalazio.it

Population Exposure to PAH Population Exposure to PAH Population Exposure to PAH Population Exposure to PAH

Population Exposure to PAH

Population Exposure to PAH Population Exposure to PAH Population Exposure to PAH Population Exposure to PAH

Population Exposure to PAH Population Exposure to PAH

Population Exposure to PAH

Population Exposure to PAH Population Exposure to PAH Population Exposure to PAH Population Exposure to PAH

Population Exposure to PAH

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EXECUTIVE SUMMARY

This technical report describes the work carried out under actions 3.3 of the Population Exposure to PAH (EXPAH) LIFE+ project. The aim of action 3.3 was to measure several air pollutants (PAHs, PM_2.5mass and PM_2.5chemical composition and ancillary gaseous toxicants data) in different living/working microenvironments to provide data of population exposure and to support modeling studies for a wider urban population exposure. Personal exposure measurements on children and elderly people were also included in the study. Three Institutes (CNR-IIA, INAIL, ARPALazio) carried out the field campaigns. The methodology was based on active sampling at low volume condition on PTFE filters and gas chromatography/mass spectrometry determination of PM2,5- bound PAH‟s non-volatile congeners, characterized by higher carcinogenic and mutagenic potencies. According to the experimental design, two seasonal in-field campaigns (summer and winter-spring) were performed by sampling both indoor and outdoor living/working microenvironments. In each seasonal campaign, 20 living environments have been monitored including two cars, one bus, six schools, two offices and nine houses. In addition, three urban monitoring stations (ARPA Stations) have been also monitoring PM2,5 and associated PAH's non- volatile congeners during the in-field sampling periods. The main effort was focused on the carcinogenic PAHs, namely benz(a)anthracene, benzo(b)fluoranthene, benzo(j)fluoranthene, benzo(k)fluoranthene, benzo(a)pyrene, indeno(1,2,3-cd)pyrene, dibenz(a,h)anthracene and the mutagenic benzo(ghi)perilene.

The main effort within the Action 3.3 during late 2011-2012 was in the conduction of the regular in- field campaigns. Only a limited amount of analyses was postponed to early 2013, namely: i) characterization of samples collected at ARPA Lazio stations in other days/weeks different than those scheduled for the campaigns (to provide the Partners of more information about PAH burdens in the air of Rome); ii) chemical characterizations on samples collected in duplicate, to confirm the reliability of the method; iii) analysis of historical data archives collected by CNR-IIA and still unpublished; iv) investigation of the weekend/weekday modulation; v) PAH characterization at personal level. The remaining work has ended by March 31^st, 2013.

The list of the in-field campaigns follows (with the respective time schedules):

1. Winter experiments:

Sites partner action period

1A. Schools, CNR 3.3.2/3 Nov. 28^th÷ Dec. 22^nd, 2011.

1B. Houses and office, CNR, 3.3.2/3 Jan. 16^th÷ Feb. 6^th, 2012.

1C. Bus and cars, INAIL 3.3.1 Dic.14^th÷ Mar. 30^th, 2012.

1D. REN ARPA Lazio 3.3.4 1A + 1B.

2. Late Winter - Spring experiments:

Sites partner action period

2A. Schools and office, INAIL 3.3.1 Feb. 20^th÷ Mar. 09^th, 2012.

2B. Houses, INAIL 3.3.1 Apr. 14^th÷ Apr. 28^th, 2012.

2C. Schools and office, CNR 3.3.2/3 May 14^th÷ Jun. 01^st, 2012.

2D. Schools and office, INAIL 3.3.1 May 14^th÷ Jun. 01^st, 2012.

2E. REN ARPA Lazio 3.4 2 A + 2B + 2C + 2D.

3. Summer experiments:

3A. Houses, INAIL study, June 6^th ÷Jun. 26^th, 2012.

3B. Houses, CNR study, June 29^th÷Jul. 19^th, 2012.

3C. Bus and cars, INAIL study, June 13^th ÷Aug. 7^th, 2012

3D. REN ARPA Lazio study, 3A + 3B.

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In order to have reference sites during the EXPAH measurement campaigns, samples coming from two monitoring sites of the Environmental Monitoring Network (ARPA) of Rome have been collected.

During the winter-spring in-field campaign (from December 2011 to March 2012), the average BaP detected indoors ranged from 0.94 (offices) to 1.14 (schools) ng/m³, and the respective outdoor values ranged from 1.4 and 2.0 ng/m³. Contemporarily, target PAHs ranged from 6.0 to 7.4 ng/m³ (indoors), and 8.4 to 13.2 ng/m³ (outdoors). The typical indoor/outdoor ratio was ~0.7. During the summer campaigns, lasted from May to July 2012, BaP ranged from 0.04 to 0.15 ng/m³ indoors and 0.06 to 0.19 ng/m³ outdoors; the target PAHs ranged 0.40÷1.35 ng/m³ (indoors), and 0.62÷1.52 ng/m³ (outdoors).

As for the PAHs measured in living environments, the indoor PAHs concentrations were not negligible and of likely outdoor origin. A good correlation between indoor and outdoor PAHs concentrations was found, with a scarce influence of indoor sources in the monitored living environments. In particular, the indoor/outdoor concentration ratio (IOR) at schools ranged from 0.5 to 0.93 in winter and 0.7÷0.9 in spring, depending on the congener. The same ratio was 0.50÷0.83 in winter and 0.6÷0.9 in spring/ summer in the houses. At the offices, the IOR was equal to 0.35÷0.70 in winter, and 0.50÷0.86 in spring.Therefore, the “PAH-associated” pollution was lower indoors than outdoors. The PAHs exposure measured at the living environments was found to be of the same order of magnitude of that recorded at ARPA stations.These IOR variabilities might be dued to different aspects such as: PM size distribution, etherogenities of building characteristics, penetration efficiency, air exchange rates and decay rates.

As for the vehicles in the public transport, exposure to PAH level is similar to that typically observed in outdoor air, whilst in the cars the indoor exposure can exceed the outdoor one.

Therefore, the contribution of vehicles concentrations cannot be neglected in assessing people exposure to air contaminants in urban area.

The main chemical components of PM2.5 (main elements, ions, elemental carbon, organic carbon) have been individually determined in both indoor and outdoor atmosphere at the three schools, during both the winter and the summer period. The analytical results were re-arranged in order to estimate the weight of the main five PM2.5 macro-sources: soil, sea, combustion processes, secondary reaction in the atmosphere, production of primary and secondary organics. Daily differences in individual components and in macro-sources were evaluated between winter and summer and between indoor and outdoor atmosphere. Winter results show that PM2.5 is mainly composed of organic and primary anthropogenic species with a lower contribution of natural sources (soil and sea-salt). In summer, the contribution of the organic and the combustion sources are lower when compared to the winter period. During both the summer and the winter period of low concentration, organics and soil components showed a substantial increase in indoor air with respect to outdoor. These components are probably due to the presence and the movements (dust re- suspension) of the students inside the classrooms. During the winter high-concentration period, this increase is still visible for soil components, while for organics it is hidden by the noticeable increase in outdoor concentration that occurs during atmospheric stability periods (role of secondary reactions during the ageing of the air masses). In addition, an increase of the contribution of crustal elements in indoor environment with respect to the outdoor mean values is observed. During the winter study the I/O ratio of PM concentration was about 0.8, as a consequence of the low ventilation of the buildings, which reduce the infiltration of outdoor pollutants. During the summer, instead, this I/O ratio was considerably higher (>1). During this period of very low outdoor concentration, in fact, the relative weight of indoor sources increases, in spite of the higher ventilation of indoor environments.

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The personal exposure to BaP resulted well below the reference value of 1ng/m³ (EU Air Quality), ranging from 0.06 ng/m³ to 0.16 ng/m³. The average ΣPAHs ranged between 0.45 ng/m³ and 1.08 ng/m³. The exposure was mainly occurring in indoor environments, such as schools and houses, and no significant differences in exposure were observed between elderly and children; moreover, exposure data resulted consistent with indoor concentrations registered at schools and homes in the same periods.

As for VOCs, the contents of benzene and its homologues in the air varied widely but never exceeded the European guideline value of 5 µg/m³. Usually the values were lower indoors, but important exceptions occurred suggesting the use of customer products (ethylbenzene, o-xylene) or the presence of tobacco smokers (benzene). Nitrogen dioxide was roughly equal indoors and outdoors, whilst indoor ozone was all-the-time lower than outdoors.

In conclusion, the EXPAH PAHs and PM_2.5 monitoring study has provided evidence about the air quality in living and working environments. It has been demonstrated that increased concentrations of PM2.5 and aerosol embedded PAHs can be found in homes, schools, and offices as well as in- vehicle transport systems. The main origin of these pollutants is from outdoor ambient air. The infiltration factor depends on the pollutants, the environment, and the season. Episodes of indoor concentrations higher than the legal limit (1 ng/m³) have been observed for the most cancerogeneous PAH (BaP), although in the monitored periods its average value was below this limit.

NOMENCLATURE

Along this Report, all symbols adopted for individual PAHs and sampling points (both special EXPAH sites and ARPA Lazio stations) defined in the Inception Report and all previous documents have been maintained unaltered.

They are:

a. Symbols:

limit of detection L.O.D.

limit of quantification L.O.Q.

not evaluated n.e.

weekend w.e.

week day (working day) w.d.

b. PAHs:

benz[a]anthracene BaA

benzo[b]fluoranthene BbF

benzo[j]fluoranthene BjF

benzo[k]fluoranthene BkF

BbF + BjF BbjF

BjF + BkF BjkF

BbF + BjF + BkF BbjkF

benzo[e]pyrene BeP

benzo[a]pyrene BaP

benzo[g,h,i]perylene BPE

chrysene+triphenylene CH

dibenz[a,h]anthracene DBahA

dibenz[a,c]anthracene DBacA

dibenz[a,j]anthracene DBajA

indeno[1,2,3-cd]pyrene IP

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perylene PE

carcinogenic PAHs cPAHs

sum of all measured PAHs PAHs cPAHs + BPE + CH (genotoxic PAHs) gPAHs cPAHs + BPE (congeners measured

by INAIL) PAHs1

BaP/BeP conc. ratio BaP/BeP

BaP/PAHs conc. ratio BaP/PAHs

c. VOCs (mono-aromatic hydrocarbons)

benzene Bz

toluene Tol

ethylbenzene EBz

meta/para-xylene (sum) mpXy

ortho-xylene oXy

total VOCs BTEX

benzene/toluene ratio Bz/Tol

d. Sites – ARPA Lazio network:

Cinecittà (Belloni) BEL

Cipro CYP

Fermi FER

Francia FRA

Castel di Guido CGU

Montelibretti MLI

Malagrotta MAG

Tenuta del Cavaliere TCA

Villa Ada VAD

Colleferro CFE

Ciampino CIA

Civitavecchia CIV

Guidonia GUI

e. Sites: Houses, schools, offices:

A. Cecinato house HAC

C. Balducci house HCB

C. Perrino house HPE

F. Troiano house HTR

P. Romagnoli house HPR

M. Di Basilio house HDB

M. Gherardi house HGH

A. Mansi house HMA

A. Militello house HMI

G. Tranfo house HTN

A. Manzi Inst. IAM

Don Bosco Inst. IDB

Don Rua Inst. IDR

G.B. Vico Inst. IVI

Immacolata Inst. ICO

La Sale Inst. ILS

XXV APrile Inst. IAP

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Via Urbana Office OUR

Arpa Office ARP

f. Sites: microenvironments:

Bus 90 express Bus

Car Citroen Xsara Picasso Car 1 Car Nissan Almera Car 2

Gym in Rome Gym

g. Locations:

indoor IN

outdoor OUT

rush traffic station tra.

residential area station res.

urban background station u.bd.

regional background station re.bd.

Notes:

A. Compounds were not evaluated since large interferences occurred.

B. Since the PAH range measured by CNR was wider than that by INAIL, the “PAHs1” quantity was introduced to uniform the results. Analogously, the sum of the three benzofluoranthene isomers is reported as BbjkF in all Tables.

C. The HPR site replaced HTR, unavailable for the summer campaign.

Figures I.1 - I.5 report the city map with EXPAH study sites and examples of in-field samplings.

Figure I.1. Map of Rome showing the sampling sites chosen for the Life+ EXPAH Project

Figure I.2. Examples of in-field sampling at school

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Figure I.3. Examples of in-field sampling at houses

Figure I.4. Examples of in-field sampling at bus

Figure I.5. Examples of in-field sampling at cars

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Index

Executive summary p. 02

Index p. 08

&1. Winter CNR-IIA in-field campaign: PAH and PM2.5 measurements in schools, houses and an office

1.1. PAHs

1.1.1. Schools p. 13

1.1.2. Houses and Office p. 16

1.1.3. Figures p. 19

1.2. PM2.5

1.2.1. Schools p. 20

1.2.3. Figures p. 22

&2. Winter INAIL in-field campaign: PAH and PM_2.5 measurements in schools and an office 2.1. PAHs

2.1.1. Schools and Office p. 24

2.1.2. Figures p. 26

2.2. PM2.5

2.2.2. Figures p. 28

&3. Winter INAIL in-field campaign: PAH and PM2.5 measurements in motor vehicles 3.1. PAHs

3.1.1. Bus p. 30

3.1.2. Cars p. 32

3.1.3. Figures p. 33

3.2. PM_2.5

3.2.1. Bus p. 36

3.2.2. Cars p. 37

3.1.3. Figures p. 37

&4. Winter CNR-IIA in-field campaign: measurements of water-soluble ions, elements, organic carbon (OC) and elemental carbon (OC) in schools and office.

4.1. Daily concentrations in schools and office p. 39

4.2. Day-by-day and average composition in schools p. 47

&5. Spring INAIL in-field campaign: PAH and PM_2.5 measurements in houses 5.1. PAHs

5.1.1. Experimental and results p. 51

5.1.2. Figures p. 53

5.2. PM2.5

5.2.1. Experimental and results p. 53

5.2.2. Figures p. 54

&6. Spring CNR in-field campaign: PAH and PM2.5 measurements in schools and an office 6.1 PAHs (Action 3.3.2)

6.1.1. Experimental and Results p. 55

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6.1.2. Figures p. 58 6.2 PM2.5

6.2.2. Figures p. 60

&7. Spring INAIL in-field campaign: PAH and PM2.5 measurements in schools and office 7.1. PAHs

7.1.2. Figures p. 64

7.2. PM2.5

7.2.2. Figures p. 65

&8. Summer INAIL in-field campaign: PAH and PM_2.5measurements in houses 8.1. PAHs

8.1.2. Figures p. 68

82. PM_2.5

8.2.2. Figures p. 70

&9. Summer CNR in-field campaign: PAH and PM2.5 measurements in houses 9.1. PAHs

9.1.2. Figures p. 74

9.2. PM2.5

9.2.2. Figures p. 76

&10. Summer INAIL in-field campaign: PAH and PM2.5 measurements in motor vehicles 10.1. PAHs

10.1.1. Bus p. 77

10.1.2. Cars p. 78

10.1.3 Figures p. 80

10.2. PM_2.5

10.2.1. Bus p. 83

10.2.2. Cars p. 83

10.2.3 Figures p. 84

&11. Ancillary measurements relative to the spring in-field experiment: PAH and PM2.5 in Rome at a gym pool

11.1. PAHs p. 85

11.1.1 Figures p. 85

11.2 PM_2,5 p. 86

11.2.1 Figures p. 86

&12. Ancillary measurements relative to the in-field experiments: PAHs at the ARPA Lazio stations

12.1. Winter in-field campaign

12.1.2. Figures p. 91

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12.2. Spring in-field campaign

12.2.2 Figures p. 98

12.4. Summer in-field campaign

12.3.2 Figures p. 104

&13. Winter CNR in-field campaign: Monitoring of mono-aromatic hydrocarbons (benzene, toluene, ethylbenzene, m/p-xylene and o-xylene), nitrogen dioxide and ozone

13.1. Mono-aromatic hydrocarbons

13.1.1. Schools p. 105

13.1.3. Figures p. 106

13.2. Nitrogen dioxide and ozone

13.2.1. Nitrogen Dioxide p. 108

13.2.3. Ozone p. 108

&14 Spring and summer CNR in-field campaigns: Monitoring of mono-aromatic hydrocarbons (benzene, toluene, ethylbenzene, m/p-xylene and o-xylene), nitrogen dioxide and ozone 14.1. Mono-aromatic hydrocarbons

14.1.1. Schools and office p. 109

14.1.2. Houses p. 109

14.1.3. Figures p. 110

14.2. Nitrogen dioxide and ozone

14.2.2. Houses p. 111

14.3. Comparison NO2 and O3 at ARPA Lazio stations p. 112

&15. Summer CNR-IIA in-field campaign: measurements of water-soluble ions, elements, organic carbon (OC) and elemental carbon (OC) in schools and office.

15.1. Daily concentrations in schools and office p. 113

15.2. Day-by-day and average composition in schools p. 121

&16. INAIL in-field experiment: personal exposure to PAHs in Rome

16.1. Study design p. 125

16.2. Sampling strategy p. 127

16.3. PAHs

16.3.1. Spring test p. 127

16.3.2. Summer test p. 131

16.4. PM2.5

16.4.1. Spring test p. 134

16.4.2. Summer test p. 136

16.5. PAH raw data p. 138

16.2. PM2.5 raw data p. 148

&17. Ancillary measurements: PAHs in Rome during periods other than those of in-field campaigns

17.1. Experimental and Results p. 153

17.1.1. Schools p. 153

17.1.2. ARPA Lazio stations p. 155

17.2. Figures p. 156

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&18. Indoor/outdoor concentration ratios of PAHs at schools, houses and offices 18.1. Schools

18.1.1. Winter campaign p. 157

18.1.2. Spring campaign p. 158

18.2. Houses

18.2.3. Summer campaign p. 160

18.3. Offices

18.4. Correlation approach

18.4.1. Schools p. 163

18.4.2. Houses p. 164

18.4.3. Offices p. 166

18.5. Motor vehicles

18.5.1. Bus p. 167

18.5.1.1. Correlation approach p. 168

18.5.1. Cars p. 169

18.5.2.1. Correlation approach p. 170

&19. Indoor/outdoor concentration ratios of PM2.5 at schools, houses, offices and motor vehicles 19.1. School

19.2. Houses

19.3. Offices

19.4. Vehicles

19.4.1 Bus p. 177

19.4.2 Cars p. 178

19.5. Correlation approach

19.5.1. Schools p. 179

19.5.2. Houses p. 180

19.5.3 Offices p. 182

19.5.4. Vehicles p. 184

&20. PAH fingerprints in emissions and in airborne PM2.5 (congener percentages)

20.1. Introduction p. 185

20.2. Industrial, vehicular and biogenic particulates: data archive analysis p. 185 20.3. Schools

20.3.1. Winter campaigns p. 188

20.3.3. Figures p. 189

20.4. Houses

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20.4.4. Figures p. 193

20.5. Offices

20.5.1. In-field campaigns p. 194

20.5.2. Figures p. 195

20.6. Benzofluoranthene isomers

&21. Winter and summer CNR-IIA in-field campaign: Indoor/Outdoor concentration ratios and

regression analysis of ions and EC/OC p. 198

&22. PAH concentrations in airborne particulates of Rome: historical data sets collected by CNR- IIA

22.1. PAHs at Montelibretti in 2005-2007 p. 200

22.2. PAHs at Villa Ada station in 2006-2007 p. 201

22.3. PAHs at ARPA Lazio stations in 2009 p. 202

22.4. PAHs at ARPA Lazio stations in 2010-2011 p. 204

22.5. PAHs at ARPA Lazio stations in winter 2011 p. 205

22.6. PAHs at Belloni station from June 2010 to May 2011 p. 207 CONCLUSIONS p. 210 ANNEX 1. Old PAHs in the airborne particulates in Rome: concentration values and partition between fine and coarse particles

A.1. PAHs in Rome in1997 p. 213

A.2. PAHs in Rome in 2000 p. 214

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&1. Winter CNR in-field campaign: PAH measurements in schools, houses and an office

1.1. PAHs

Two different sampling periods were adopted for schools and homes plus the office. The GC column allowed to distinguish BbF from BjkF.

1.1.1. Schools

According to the new in-field campaign protocol, the former regular one was performed from November 28 to December 22, 2011 in three schools, namely:

- Alberto Manzi Institute (IAM);

- Don Rua Institute (IDR);

- Gian Battista Vico Institute (IVI).

Airborne particulates were collected both indoor and outdoor, at medium- and low-volume conditions, respectively. Indoor samples were collected in common spaces among schoolrooms.

The particulate collection preliminary to PAH monitoring was made in three steps, i.e.:

- From November 28 to December 02;

- From December 12 to December 16;

- From December 19 to December 22.

Samples were pooled into five- or four-day groups and processed for PAH characterization.

To perform the Analysis, the procedure set-up during the preliminary campaign and tested through the summer 2011 inter-comparison was used (see Inception Report).

Tables 1.1-2 show the results for indoor and outdoor environments, respectively. For sake of completeness, the BbjkF, cPAHs and gPAHs quantities as well as the BaP/BeP and BaP/PAHs ratios are reported. The former is a semi-quantitative index of ambient air reactivity (i.e. of the particle “ageing”), the latter indicates the relative importance of BaP within the PAH group.

Table 1.1. Indoor concentrations of PAHs at three schools of Rome (Nov. 28 ÷ Dec. 22, 2011).

Data are reported in ng/m³ units. A) First sampling week; B) second week; C) third week

A) 1st week IAM IDR IVI

BaA 0.67 0.92 0.68

BbF 2.69 3.51 2.37

BjkF 2.52 3.31 2.20

BbjkF 5.22 6.81 2.57

BaP 2.47 3.09 1.94

IP 2.25 2.38 1.70

DBA 0.29 0.23 0.30

CH 1.22 1.54 1.20

BPE 2.80 2.54 2.15

BeP 2.09 2.67 1.90

PE 0.49 0.57 0.44

PAHs 17.5 20.8 14.9

cPAHs 10.9 13.4 9.2

PAHs1 13.7 16.0 11.3

BaP/BeP 1.18 1.16 1.02

BaP/PAHs 0.14 0.15 0.13

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B) nd week IAM IDR IVI

BaA 0.23 0.20 0.28

BbF 0.66 0.71 0.61

BjkF 1.13 1.08 1.31

BbjkF 1.78 1.79 1.92

BaP 0.68 0.64 0.79

IP 0.73 0.40 1.02

DBA 0.12 0.12 0.13

CH 0.49 0.47 0.69

BPE 1.04 1.02 1.70

BeP 0.69 0.74 0.89

PE 0.24 0.12 0.20

PAHs 6.0 5.5 7.6

cPAHs 3.6 3.5 6.0

PAHs1 4.6 4.8 7.7

BaP/BeP 0.99 0.86 0.89

BaP/PAHs 0.11 0.12 0.10

C) 3rd week IAM IDR IVI

BaA 0.25 0.24 0.22

BbF 0.49 0.70 0.42

BjkF 1.15 1.27 1.33

BbjkF 1.65 1.96 1.75

BaP 0.72 0.75 0.65

IP 0.76 0.72 0.63

DBA 0.14 0.13 0.10

CH 0.73 0.66 0.69

BPE 1.28 0.90 0.98

BeP 0.80 0.86 0.74

PE 0.25 0.21 0.20

PAHs 6.6 6.4 6.0

cPAHs 3.5 3.8 3.4

PAHs1 4.8 4.7 4.3

BaP/BeP 0.90 0.87 0.88

BaP/PAHs 0.11 0.12 0.11

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Table 1.2. Outdoor concentrations of PAHs at three schools of Rome (Nov. 28 – Dec. 22, 2011).

Data are reported in ng/m³ units. A) First sampling week; B) second week; C) third week

A) 1st week IAM IDR IVI

BaA 1.19 1.31 1.25

BbF 4.01 3.75 4.49

BjkF 3.15 3.11 3.59

BbjkF 7.15 6.86 8.08

BaP 2.93 2.81 3.02

IP 2.30 2.36 2.34

DBA 0.31 0.35 0.29

CH 1.90 1.91 2.22

BPE 2.66 2.44 2.90

BeP 2.67 2.52 3.05

PE 0.58 0.59 0.56

PAHs 21.7 21.2 23.7

cPAHs 14.3 4.0 5.2

PAHs1 16.9 4.8 6.3

BaP/BeP 1.10 1.12 0.99

BaP/PAHs 0.14 0.13 0.13

B) 2nd week IAM IDR IVI

BaA 0.37 0.44 0.46

BbF 0.99 1.05 1.13

BjkF 0.98 1.03 1.06

BbjkF 1.98 2.07 2.19

BaP 0.77 0.78 0.87

IP 0.69 0.67 0.85

DBA 0.11 0.11 0.12

CH 0.58 0.69 0.70

BPE 0.80 0.78 1.21

BeP 0.73 0.77 0.91

PE 0.18 0.18 0.22

PAHs 6.2 6.5 7.5

cPAHs 4.0 5.2 7.8

PAHs1 4.8 6.3 9.3

BaP/BeP 1.05 1.01 0.96

BaP/PAHs 0.12 0.12 0.12

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C) 3rd week IAM IDR IVI

BaA 0.55 0.43 0.42

BbF 1.23 1.11 1.00

BjkF 1.34 1.27 1.11

BbjkF 2.67 2.37 2.11

BaP 0.96 0.86 0.74

IP 0.95 0.85 0.73

DBA 0.13 0.14 0.11

CH 1.01 0.79 0.85

BPE 1.09 0.94 0.94

BeP 0.96 0.88 0.83

PE 0.20 0.20 0.16

PAHs 8.4 7.5 6.9

cPAHs 5.2 4.7 4.1

PAHs1 6.3 5.6 5.0

BaP/BeP 1.00 0.98 0.89

BaP/PAHs 0.11 0.12 0.11

1.1.2. Houses and office

The PAH measurements were made at four private houses and in an office (representative of non- industrial work places). They were:

- The A. Cecinato house (HAC);

- The C. Balducci house (HCB);

- The C. Perrino house (HPE);

- The F. Troiano house (HTR);

- The ARPA Lazio building (ARP).

Airborne particulates were collected both indoor and outdoor, always at low-volume conditions.

Indoor samples were collected in living rooms; outdoor samples were collected in corresponding balconies.

The sampling campaign was carried out in January and February 2012 and comprised three five-day intervals:

- from January 16 to January 20, 2012;

- from January 23 to January 27, 2012;

- from January 30 to February 3, 2012.

Particulates were pooled into five-day groups and processed as “weekly samples” for PAH characterization. Tables 1.3-4 show the results for indoor and outdoor environments, respectively.

For sake of completeness, the BaP/BeP and BaP/PAHs ratios are also reported.

In some cases the separation between benzofluoranthene isomers could not be obtained; thus only the sum of the three compounds is reported. The analysis failed for the second week at the HAC site.

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Table 1.3. Indoor concentrations of PAHs at four houses and an office of Rome (Jan 16 ÷ Feb 03, 2012). Data are reported in ng/m³ units. A) First sampling week; B) second week; C) third week

A) 1^st week HAC HCB HPE HTR ARP

BaA 0.24 0.57 0.18 0.28 0.24

BbF 0.93 1.89

3.45 1.32 1.33

BjkF 1.78 2.69 2.01 1.93

BbjkF 2.71 3.58 3.45 3.32 3.26

BaP 1.14 2.13 1.30 1.48 1.24

IP 1.71 2.40 1.53 2.28 1.97

DBA 0.19 0.30 0.18 0.25 < L.O.D.

CH 0.49 1.15 0.57 0.61 0.73

BPE 2.16 2.63 1.82 3.32 2.33

BeP 1.21 1.96 1.52 1.60 1.36

PE 0.29 0.49 0.50 0.37 0.68

PAHs 10.1 16.2 11.1 13.5 11.8

cPAHs 6.0 10.0 6.6 7.6 6.7

PAHs1 8.1 12.6 8.5 10.9 9.0

BaP/BeP 0.94 1.09 0.85 0.92 0.91

BaP/PAHs 0.11 0.13 0.12 0.11 0.10

B) 2^nd week HAC HCB HPE HTR ARP

BaA 0.14 0.30 0.12 0.17 0.10

BbF 2.08 0.99

2.26 0.80 0.79

BjkF 2.09 1.52 1.31

BbjkF 2.08 3.08 2.26 2.31 2.10

BaP 0.79 1.29 0.82 1.06 0.75

IP 1.11 1.48 1.22 1.61 1.06

DBA 0.18 0.20 0.15 0.18 < L.O.D.

CH 0.39 0.71 0.40 0.39 0.45

BPE 1.35 1.81 1.54 2.59 1.19

BeP 1.12 1.31 0.99 1.22 0.90

PE 0.30 0.24 0.37 0.31 0.35

PAHs 7.4 10.4 7.9 9.8 6.9

cPAHs 4.3 6.4 4.6 5.3 4.0

PAHs1 5.6 8.2 6.1 7.9 5.2

BaP/BeP 0.70 0.99 0.83 0.87 0.84

BaP/PAHs 0.11 0.12 0.10 0.11 0.11

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C) 3^rd week HAC HCB HPE HTR ARP

BaA 0.14 0.16 0.09 0.13 0.08

BbF 1.03 0.53

1.01 0.44 0.47

BjkF 1.01 0.96 0.81

BbjkF 1.03 1.54 1.01 1.39 1.27

BaP 0.43 0.56 0.33 0.44 0.35

IP 0.68 0.91 0.76 1.03 0.48

DBA 0.11 0.12 0.10 0.13 < L.O.D.

CH 0.38 0.46 0.24 0.33 0.26

BPE 0.71 1.02 0.98 1.42 0.77

BeP 0.51 0.71 0.48 0.63 0.54

PE 0.14 0.16 0.21 0.18 0.32

PAHs 4.1 5.6 4.2 5.7 4.1

cPAHs 2.4 3.3 2.3 3.1 2.2

PAHs1 3.1 4.3 3.3 4.5 2.9

BaP/BeP 0.85 0.79 0.68 0.70 0.64

BaP/PAHs 0.10 0.10 0.08 0.08 0.08

Table 1.4. Outdoor concentrations of PAHs at four houses and an office investigated in Rome (Jan 16 ÷ Feb 03, 2012). Data are reported in ng/m³ units. A) First sampling week; B) second week; C) third week.

A) 1^st week HAC HCB HPE HTR ARP

BaA 1.09 1.51 0.43 1.16 1.80

BbF 9.97 2.67

3.19 2.53 4.85

BjkF 3.86 3.64 10.71

BbjkF 9.97 6.52 3.19 6.17 15.55

BaP 3.36 2.55 0.81 2.55 4.00

IP 3.94 3.14 1.97 2.93 4.21

DBA 0.53 0.36 < L.O.D. 0.33 1.04

CH 2.69 2.39 1.20 2.19 5.70

BPE 4.97 3.48 2.29 3.90 4.52

BeP 3.75 2.40 1.83 2.53 4.64

PE 1.09 0.59 0.63 0.70 1.56

PAHs 31.4 22.9 12.3 22.5 43.0

cPAHs 18.8 14.1 5.9 13.1 26.6

PAHs1 23.8 17.6 8.2 17.0 31.1

BaP/BeP 0.90 1.07 0.44 1.01 0.86

BaP/PAHs 0.11 0.11 0.07 0.11 0.09

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B) 2^nd week HAC HCB HPE HTR ARP

BaA n.e. 0.71 0.21 0.93 0.67

BbF n.e. 1.47

2.89 1.88 2.56

BjkF n.e. 2.29 3.55 3.70

BbjkF n.e. 3.75 2.89 5.43 6.25

BaP n.e. 1.49 0.58 1.94 1.93

IP n.e. 2.02 1.07 2.34 2.55

DBA n.e. 0.24 < L.O.D. 0.24 0.63

CH n.e. 1.24 0.72 2.01 3.12

BPE n.e. 2.32 3.48 3.53 3.14

BeP n.e. 1.51 1.23 2.48 2.24

PE n.e. 0.34 0.64 0.54 1.03

PAHs n.e. 13.6 10.8 19.4 21.6

cPAHs n.e. 8.2 4.2 10.9 12.0

PAHs1 n.e. 10.5 7.7 14.4 15.2

BaP/BeP n.e. 0.98 0.47 0.78 0.86

BaP/PAHs n.e. 0.11 0.05 0.10 0.09

C) 3^rd week HAC HCB HPE HTR ARP

BaA 0.15 0.25 0.11 0.17 0.18

BbF 1.43 0.74 0.82 0.96 1.26

BjkF 1.39 1.28 1.27 1.88

BbjkF 1.43 2.13 2.10 2.23 3.13

BaP 0.42 0.68 0.49 0.75 0.91

IP 0.73 0.91 0.79 1.18 1.41

DBA 0.10 0.14 < L.O.D. 0.184 < L.O.D.

CH 0.42 0.67 0.64 0.40 1.30

BPE 1.05 1.08 0.92 1.73 1.85

BeP 0.57 0.84 0.87 1.06 1.26

PE 0.23 0.20 0.23 0.28 0.42

PAHs 5.1 6.9 6.1 8.0 10.5

cPAHs 2.8 4.1 3.5 4.5 5.6

PAHs1 3.9 5.2 4.4 6.2 7.5

BaP/BeP 0.74 0.80 0.57 0.71 0.73

BaP/PAHs 0.08 0.10 0.08 0.09 0.09

1.1.3. Figures

Figure 1.1 summarizes the PAH concentration values obtained in the three schools investigated by CNR-IIA, namely AM, IDR, IVI. Similarly, Figure 1.2 shows the average concentrations of individual PAH congeners recorded over the whole campaign at houses and office, indoors and outdoors, and the respective indoor/outdoor concentration ratios.

Figure 1.1. Average PAH concentrations recorded at IAM, IDR and IVI from Nov. 28^th to Dec.

22^nd, 2011. A) indoor; B) outdoor. Data in ng/m³.

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Figure 1.2. Average PAH concentrations recorded at HAC, HCB, HPE, HTR and ARP during Jan.

16^th ÷ Feb 03^rd, 2012. A) indoor; B) outdoor. Data in ng/m³.

1.2. PM2.5

PM_2.5was collected both indoors and outdoors at all sites investigated to perform the airborne PAH evaluations. Since the collection filters were replaced each day, the procedure adopted allowed to determine the average daily PM2.5 concentrations, by conditioning and weighting the membranes with automatic micro-balance.

1.2.1. Schools

Table 1.5 shows the average daily concentrations of PM2.5 at the three schools investigated, namely Alberto Manzi (IAM), Don Rua (IDR) and Gian Battista Vico (IVI) Institutes. The sets appear

B A

A

B

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incomplete, due to break of some filters during sampling. Nevertheless, the indoor/outdoor comparison could be made for all sites. Since the outdoor collection of PM was made through automated sequential samplers, the corresponding PM2.5 values could be determined also during the week ends, as ancillary environmental information to Partners.

Table 1.5. Average daily concentrations of PM2.5 at three schools of Rome. November to December 2011. Numbers in µg/m³.

site IAM IDR IVI

date IN OUT IN OUT IN OUT

Nov. 28 37 43 42 57 1102 42

Nov. 29 43 57 59 68 49 52

Nov. 30 36 49 43 55 37 47

Dec. 01 42 53 59 65 42 51

Dec. 02 34 45 32 65 50 53

Dec. 03 n.e. 10 n.e. 24 n.e. 11

Dec. 04 n.e. 7 n.e. 8 n.e. 8

Dec. 12 11 11 13 17 14 n.e.

Dec. 13 20 31 28 n.e. 27 n.e.

Dec. 14 12 13 14 20 14 14

Dec. 15 13 17 15 11 15 19

Dec. 16 5 7 7 12 12 9

Dec. 17 n.e. 22 n.e. 16 n.e. 22

Dec. 18 n.e. 14 n.e. 20 n.e. 16

Dec. 19 10 11 15 11 13 10

Dec. 20 n.e. 22 n.e. 19 n.e. 21

Dec. 21 7 24 n.e. 23 n.e. 19

Dec. 22 9 16 13 23 10 10

average 21 28 27 34 24 29

std. dev. 15 18 18 23 16 18

1.2.2. Houses and office

Table 1.6 shows the average daily concentrations of PM_2.5at the four houses and the work place investigated, namely A. Cecinato (HAC), C. Balducci (HCB), C. Perrino (HPE) and F. Troiano (HTR) homes, and the ARPA Lazio building (ARP). Also in this case some filter breaks hindered to have the full sets of data, although the indoor/outdoor comparison could be made for all sites.

Since the outdoor collection of PM was made through automated sequential samplers, the corresponding PM2.5 values could be determined also during the week ends, as ancillary environmental information to Partners.

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Table 1.6. Average daily concentrations of PM_2.5at four houses and a work place of Rome. January to February 2012. Numbers in µg/m³. IN: indoor; OUT: outdoor; n.e. = not evaluated.

site ARP HAC HCB HPE HTR

date IN OUT IN OUT IN OUT IN OUT IN OUT

Jan. 16 12 31 31 29 39 n.e. 23 24 29 27

Jan. 17 21 63 38 45 56 51 28 37 33 42

Jan. 18 29 77 41 67 82 61 42 57 42 64

Jan. 19 16 n.e. 36 n.e. 95 63 38 37 47 62

Jan. 20 17 n.e. 31 40 61 26 30 24 31 28

Jan. 23 17 n.e. 32 n.e. 46 38 34 34 35 34

Jan. 24 11 21 32 n.e. 30 18 25 15 18 13

Jan. 25 9 15 29 n.e. 21 11 20 10 14 10

Jan. 26 21 37 31 30 37 27 22 20 21 21

Jan. 27 20 60 38 n.e. 72 45 42 44 38 48

Jan. 30 5 25 33 29 45 19 24 n.e. 23 20

Jan. 31 16 51 28 n.e. 36 32 n.e. n.e. 34 28

Feb. 01 9 n.e. 16 n.e. 36 15 n.e. n.e. 34 10

Feb. 02 11 30 24 26 54 27 n.e. n.e. n.e. 33

Feb. 03 10 14 26 n.e. 43 13 n.e. n.e. n.e. n.e.

average 15 39 31 38 50 32 30 30 31 31

std. dev. 6 21 6 14 20 17 8 14 9 17

The average outdoor concentrations of PM_2.5over the whole period (31÷39 µg/m³) were more similar than the corresponding indoors (15÷50 µg/m³). The maximums were detected indoors at HCB (average: 50 µg/m³; peak: 95 µg/m³).

By cutting off the “outlier” value of 67 µg/m³ recorded on Jan. 18^th, the average PM_2.5concentration and its standard deviation dropped to 33 and 7 µg/m³, respectively.

1.2.3. Figures

Figure 1.3A/B shows the average daily PM2.5 concentrations recorded during the winter campaign at schools (Nov. ÷ Dec. 2011). Airborne particulates were richer in the first week of sampling compared to the other two ones. Moreover, the day-to-day modulations were similar at all sites.

Figure 1.3. Daily concentrations of PM2.5 (µg/m³) at the three schools; A) indoor; B) outdoor.

A

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Figure 1.4A/B and Figure 1.5 report, respectively, the PM_2.5concentrations detected both indoors and outdoors at the four homes and at the office from Jan. 16^th to Feb. 3^rd, 2012. The highest PM_2.5 values were recorded at HCB indoors, where spotty tobacco smog episodes occurred.

Figure 1.4. Daily PM2.5 at the four homes in Rome. A) indoor; B) outdoor. Data in µg/m³ units.

Figure 1.5. Daily PM2.5 at the office during the winter campaign. Concentration as µg/m³.

B

A

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&2. Winter INAIL in-field campaign: PAH and PM2.5 measurements in schools and an office

2.1. PAHs

2.1.1. Schools and Office

According to the in-field campaign protocol, the winter campaign was performed from February 14 to March 9, 2012 in three schools and in one office (representative of non-industrial work places), namely:

La Salle Institute (ILS);

Circolo XXV Aprile Institute (IAP);

Istituto Immacolata (ICO);

Via Urbana office (OUR).

Airborne particulates were collected both indoor and outdoor, at low-volume conditions. Indoor samples were collected in common spaces among schoolrooms, as far as La Sale and Immacolata Institutes are concerned, whilst, due to logistic problems, in the XXV Aprile Institute they were collected inside a classroom used as scientific laboratory but not much frequented, with door and windows closed for most of the time. In the office, indoor samples were collected in a “high populated” room, with natural and artificial ventilation.

The particulate collection preliminary to PAH monitoring was made in four steps, i.e.:

- From February 14to February17 (ILS + IAP + OUR);

- From February 20 to February 24 (ILS + IAP + ICO + OUR);

- From February 27 to March 2 (ILS + IAP + ICO + OUR);

- From March 5 to March 9 (ICO).

Samples were pooled into five- or four-days groups and processed for PAH characterization.

To perform the analysis, the procedure set-up during the preliminary campaign and tested through the summer 2011 inter-comparison was used (see Inception Report).

Tables 2.1-2.2 show the results for indoor and outdoor environments, respectively. For sake of completeness, the BaP/PAHs1 ratios are also reported: it indicates the relative importance of BaP within the PAHs1 group.

Table 2.1. Indoor concentrations of PAHs at three schools of Rome (Feb.14 – Mar. 9, 2012) . Data are reported in ng/m³ units. A) First sampling week; B) second week; C) third week; D) fourth week.

A) 1st week ILS IAP ICO OUR

BaA 0.40 0.13 - 0.39

BbjkF 1.87 0.57 - 3.24

BaP 1.52 0.38 - 2.10

IP 1.69 0.56 - 2.02

DBahA 0.20 0.07 - 0.33

BPE 1.42 0.44 - 2.04

PAHs1 7.10 2.15 - 10.13

BaP/PAHs 0.21 0.18 - 0.21