Marie-Jeanne Teil
email: marie-jeanne.teil@upmc.fr

Elodie Moreau-Guigon

Martine Blanchard

Fabrice Alliot

Johnny Gasperi

Mathieu Cladière

Corinne Mandin

Sophie Moukhtar

Marc Chevreuil

Endocrine disrupting compounds in gaseous and particulate outdoor air phases according to environmental factors

Keywords: endocrine disrupting compounds, semi-volatile organic compounds, outdoor air, gaseous phase, particulate phase

This study investigated, for the first time in France, the spatial and temporal patterns of 55 endocrine disrupting chemicals (EDCs) in ambient air at three sites (urban, suburban and forest) under two climatic periods (warm/cold) for 2 successive years. All EDCs, except tetrabromobisphenol A (TBBPA), were encountered with various frequencies of up to 100%. Phthalate diesters (PAEs) were the most abundant chemicals with total concentrations as the sum of compounds, ranging from 10 to 100 ng m -3 of total air, followed by alkylphenols (APs) and polycyclic aromatic hydrocarbons (PAHs), which were both approximately 1 ng m -3 . Polychlorinated biphenyl (PCBs) and bisphenol A (BPA) concentrations were notably lower (approximately 0.1 ng m -3 ). Air concentrations, depending on the considered compounds, were from 1.2 to 2 times higher in the urban than the suburban area and from 2 to 5 times higher in the urban than the forest site. PAH emissions were higher in the cold period, due to combustion processes. This finding is contrary to the other EDCs that are more abundant in the summer and governed by volatilisation. Most of the EDCs were largely distributed in the gaseous phase (> 80% in the summer). The octanol/air partition coefficient (K OA ) and vapour pressure (Vp) were relevant parameters for predicting EDC partitioning and direct relationships (p < 0.001) were observed i) between log K particle/gas partitioning (log Kp) and log K OA and ii) between EDC ratios in the gaseous phase and log vapor pressure (log Vp).

Highlights

EDCs in the Paris area were similar to Western countries except PAHs and PBDEs PCBs and PAEs showed an urban signature AP, PAH and PBDE sources were more distributed along a urban-suburban transect EDCs prevailed in gaseous phase whatever the season except DEHP and heavy PAHs

Introduction

The continuous release of a number of endocrine disrupting chemicals (EDCs), such as bisphenol A (BPA), tetrabromobisphenol A (TBBPA), phthalate diesters (PAEs), alkylphenols (APs), polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and polycyclic aromatic hydrocarbons (PAHs), to the environment generates new concerns regarding human exposure to low doses of toxic mixtures and possible subsequent effects on health [START_REF] Benachour | Cytotoxic effects and aromatase inhibition by xenobiotic endocrine disrupters alone and in combination[END_REF][START_REF] Woodruff | Bridging epidemiology and model organisms to increase understanding of endocrine disrupting chemicals and human health effects[END_REF].

The emission sources of these chemicals have greatly increased and diversified over the past decades [START_REF] Eea | EU emission inventory report 1990-2011 under the UNECE Convention on LRTAP[END_REF]; and therefore, they have appeared as major air contaminants, particularly because of their semi-volatile properties [START_REF] Rudel | Endocrine disrupting chemicals in indoor and outdoor air[END_REF]. Thus, PAEs, APs, PCBs and PBDEs that are not chemically bound to matrices might become easily dispersed by volatilisation [START_REF] Palm | Assessing the environmental fate of chemicals of emerging concern: a case study of the polybrominated diphenyl ethers[END_REF][START_REF] Fujii | A study on emission of phthalate esters from plastic materials using a passive flux sampler[END_REF][START_REF] Liang | Emission of Phthalates and Phthalate Alternatives from Vinyl Flooring and Crib Mattress Covers: The Influence of Temperature[END_REF].

PAEs can be emitted into the atmosphere from commonly used products, plastics, detergents, building materials or furniture [START_REF] Wormuth | What are the sources of exposure to eight frequently used phthalic acid esters in Europeans? Risk analysis: an official publication of the[END_REF]. To date, despite a wide use of BPA in polycarbonate and epoxy resin production, emission sources and subsequent impacts upon ambient air quality remain poorly documented [START_REF] Huang | Bisphenol A (BPA) in China: a review of sources, environmental levels, and potential human health impacts[END_REF].

APs are by-products of alkylphenol ethoxylates largely used in household detergents. The European directive 2003/53/EC that came into force in January 2005 restrained the use of products containing more than 0.1% nonylphenols (NP) or nonylphenol ethoxylates.

However, alkylphenol ethoxylates are still applied as dispersing agents in pulp and paper production, emulsifying agents in latex paints, glue and pesticides or in the preparation of antioxidants, curing agents and heat stabilisers for polymer resins and may be emitted to the environment from building materials [START_REF] Saito | Indoor air pollution by alkylphenols in Tokyo[END_REF].

PBDEs, a major class of flame retardants used in a number of manufactured goods to reduce their flammability, were composed of three major commercial formulations: penta-BDE, octa-BDE and deca-BDE [START_REF] De Wit | Brominated flame retardants in the Arctic environment --trends and new candidates[END_REF]. Since 2003, penta-and octa-BDE were banned of use in all applications for the European Union market (Directive2003/11/EC) Deca-BDE was registered under the "Registration, Evaluation, Authorisation and Restriction of Chemicals" (REACH) in 2010 and thus its uses have been restricted to applications such as automotive equipment, textiles and construction and suppressed for electric and electronic equipment (Deca-BDE, 2012). Tetrabromobisphenol A (TBBPA) is used as a reactive or additive flame retardant in polymers such as ABS, epoxy and polycarbonate resins, polystyrene, phenolic resins or adhesives [START_REF] Who | Environmental Health Criteria 172. Tetrabromobisphenol A and derivatives International Program on Chemical Safety[END_REF].

Chlorinated compounds such as hexachlorobenzene (HCB) and PCBs have been classified as persistent organic pollutants in the 1998 Aarhus Protocol (Aarhus, 24 June 1998), in the framework of the Geneva Convention on long-range transboundary air pollution.

Dispersive uses of PCBs were banned in France by the Decree of 8 July 1975 and their uses were restricted to in-service equipment by a second decree in February 1986. Finally, in February 2003, a decree on the elimination of all equipment containing PCBs before the end of 2010 has been published. An unknown stock of PCBs is within now buried landfills and other waste-handling facilities as well as diffuse sources such as electrical wiring and paints (Diamond et al, 2010). Most recently, new "non-aroclor" PCBs were detected as byproduct of diarylide yellow [START_REF] Rodenburg | Evidence for Unique and Ubiquitous Environmental Sources of 3,3′-Dichlorobiphenyl (PCB 11)[END_REF] and other pigment production [START_REF] Anezaki | Polychlorinated biphenyl contamination of paints containing polycyclic-and Naphthol AS-type pigments[END_REF].

Although HCB production has ceased since 1993, this compound is still being generated inadvertently as a by-product and/or an impurity in several chemical processes [START_REF] Bonnomet | Hexachlorobenzene. Ineris[END_REF] and pentachlorobenzene (PeCB) occurs as a by-product of HCB degradation [START_REF] Brignon | Pentachlorobenzene. INERIS[END_REF].

PAHs are continuously produced by combustion processes, mainly from domestic heating and automobile traffic [START_REF] Katsoyiannis | PAH molecular diagnostic ratios applied to atmospheric sources: a critical evaluation using two decades of source inventory and air concentration data from the UK[END_REF][START_REF] Tobiszewski | PAH diagnostic ratios for the identification of pollution emission sources[END_REF]. Despite PAHs are not considered as POPs, they were included to the Aarhus protocol. The objective was to reduce their emissions from stationary sources below their levels in 1990. For the emission inventories, the four indicator compounds shall be used: benzo(a)pyrene, benzo(b)fluoranthene, benzo(k)fluoranthene, and indeno(1,2,3-cd)pyrene.

Consequently, EDCs might undergo local or long range transport and their residence time in the air depends on climatic conditions and pollutant partitioning between the gaseous and particulate phases [START_REF] Wania | Assessing the potential of persistent organic chemicals for long-range transport and accumulation in polar regions[END_REF].

This study investigated for the first time in France, the atmospheric fate of a wide variety of EDCs (n=55) including PCBs, PBDEs, PAHs, APs, PAEs, HCB, PeCB, BPA and TBBPA, and considering both their gaseous and particulate phases. The target compounds were selected according to suspicion of endocrine disrupting properties, to their classification as POPs and semi-volatile organic compounds and to their environmental occurrence. The concentration levels for the different EDC families were first considered, in order to highlight the general trends of EDC distribution in France and to compare with the contamination in other countries. As EDCs result from various sources, the spatial variations between three sites located respectively in urban, suburban and forest areas were studied. In addition, temporal variations between two contrasted seasons with and without domestic heating and between two successive years were investigated. Next, the particle/gas partitioning was examined on the basis of compound molecular properties. Last, relationships between outdoor temperature, suspended particles < 10 µm (PM10) and EDC air concentrations were explored at the most polluted site.

Material and Methods

Sampling schedule

The three sampling sites belonged to the local air monitoring network of the Ile-de-

Sample collection and treatment

The particulate phases were sampled onto quartz fibre filters (porosity 0.3 µm supplied by Whatman) and gaseous phases onto XAD-2 resin (20-60 mesh). The resin from Sigma-Aldrich (Saint-Quentin Fallavier, France) was cleaned and dried under vacuum, and 75 g were introduced into two brass cartridges (2 cm diameter; 20 cm length). The filters were put on open aluminium filter holders (Ecomesure, Janvry, France) and used in total suspended particle mode [START_REF] Granier | Behaviour and spatial and temporal variations of polychlorinated biphenyls and lindane in the urban atmosphere of the Paris area, France[END_REF]. The sampler (filter and resin) was connected to a sampling pump (Busch, model SV1005GP) with a paddle dryer combined with a timer and an air flow meter (Hivolin, Germany). To secure the trapping of all EDCs, air speed through the system was < 170 cm s -1 as stated in the IEPA method (IEPA/APC/ 1985). The air flow in the sampler remained constant, from 1.2 to 1.8 m 3 h -1 (Table SM.1). The outdoor temperatures and the concentrations of particulate matter < 10 μm in diameter (PM10) were supplied by Airparif (Table SM.1).

The entire experimental procedures (sampling + clean-up + fractionation) and validations for sampling, extraction and analytical methods (Tables SM.2 to SM.7) were previously described [START_REF] Alliot | A multi-residue method for characterization of endocrine disruptors in gaseous and particulate phases of ambient air[END_REF]. The XAD-2 resins and filters were extracted separately. An aliquot of each extract was kept for AP analyses using a method previously developed [START_REF] Cladière | Alkylphenolic compounds and bisphenol A contamination within a heavily urbanized area: case study of Paris[END_REF]. Laboratory blanks were run for each series with clean XAD-2 resins and clean filters (matrix blank). They were subtracted from sample values. Internal standards were added to samples prior to extraction and compounds were quantified by internal calibration. Syringe standards were added to vials prior to analyses to determine internal standard recoveries.

Presentation of the results

The results for each site are presented as the mean ± standard deviation (n = 6) and as the median. Mean gaseous and particulate phase concentrations (n = 3) are calculated for each season. PAEs are expressed both as individual compounds and as the sum of 7 PAEs (∑7PAEs). APs are expressed as the sum of octylphenol and 4-nonylphenols (∑OP+NP).

PCBs are expressed as ∑PCBi (the sum of 7 PCB indicators for the monitoring of PCBs in Europe: CB28,52,101,118,138,153 and 180), ∑PCB-DL (the sum of CB77,81,126,169 for the non-ortho polychlorinated dibenzo-p-dioxins-like PCBs and CB105,114,118,123,156,157,167,189 for the mono-ortho polychlorinated dibenzo-p-dioxins-like PCBs) and ∑19PCBs. PBDEs are expressed as individual compounds and as ∑8PBDEs (the sum of BDE28,47,99,100,153,154,183 and 209) dibenzo(a,h)anthracene -DahA, and benzo(g,h,i)perylene -BghiP) and as ∑15PAHs (Table SM.6).

The EDC groups were represented by compounds with low and high molecular weights to give a comprehensive view of their behaviour. Relationships between i) compounds as % in the gaseous phase and log of their vapour pressure (log Vp, Pa at 25 °C) and ii) between log K particle/gas partitioning (log Kp) and log octanol/air partition coefficient (log K OA ) were explored.

Statistical analyses of spatial and temporal variations were performed with the nonparametric test of Mann-Whitney, and correlation significances were expressed by Spearman's r coefficient at α = 0.05. A principal component analysis -PCA (XLSTAT PRO software; Copyright holder CC-BY-SA-3.0, Addinsoft, Paris, France) was used for the Paris site with a diagram sorting out the main trends of the different EDC concentrations for the two campaigns. When the measured concentration was < the limit of quantification (LOQ), the LOQ value divided by 2 was used for the mean calculation and for the PCA analysis (Decree, July 08 2010).

Results and Discussion

General trends

All of the targeted EDCs except for TBBPA were quantified in the ambient air at the urban, suburban and forest sites (Table 1 andTable 2). The patterns for each site and season are shown in Fig. 1. In decreasing order, the overall concentration (∑ of gaseous and particulate phases) trends were similar and are as follows, PAEs > APs ≥ PAHs > PCBs > BPA > HCB > PeCB > PBDEs.

PAEs were encountered in all air samples, and their concentrations ranged from 6.8 to 165 ng m -3 as the ∑7PAEs. The main compound was DEHP (from 0.1 to 156 ng m -3 ) followed by DiBP (from 3.2 to 30 ng m -3 ) and DnBP (from 0.1 to 11 ng m -3 ). These compounds were detected at a frequency of 100%. DEHP concentrations are in accordance with those previously measured in Paris (France) [START_REF] Teil | Atmospheric fate of phthalate esters in an urban area (Paris-France)[END_REF] and in the Netherlands [START_REF] Peijnenburg | Occurrence of phthalate esters in the environment of the Netherlands[END_REF].

APs and PAHs were the second most abundant EDC group (Fig. 1). OP and NP were always detected and their concentrations ranged respectively, from 0.034 to 0.657 ng m -3 and from 0.216 to 2.08 ng m -3 . NP represented the major constituent of the total APs (72 to 88%).

This is consistent with literature data i.e., NP concentrations from 0.15 to 1 ng m -3 in the gas phase and from 0.0017 to 0.117 ng m -3 in the particulate phase of ambient air in NE-Bavaria, Germany ( [START_REF] Berkner | Development and validation of a method for determination of trace levels of alkylphenols and bisphenol A in atmospheric samples[END_REF].

The ∑8PAHs were quantified in all samples with concentrations ranging from 0.215 to 1.93 ng m -3 . PAH concentrations in decreasing order were PHE > FLU > FTH (Table SM.8).

A similar sequence was observed at a suburban site located nearby in Paris in 2010 [START_REF] Motelay-Massei | Polycyclic aromatic hydrocarbons in bulk deposition at a suburban site: assessment by principal component analysis of the influence of meteorological parameters[END_REF]. Literature data are scarce for periods similar to this study. Our concentrations remained lower than those of high volume air sampling (5.3 to 71.6 ng m -3 as ∑14 PAHs) at four locations in the Chesapeake bay (USA) in 1994 [START_REF] Gustafson | Particle/Gas Concentrations and Distributions of PAHs in the Atmosphere of Southern Chesapeake Bay[END_REF] , . In Bursa (Turkey), for the period 2008-2009, residential and suburban sites showed average concentrations of respectively, 77 and 30 ng m -3 as ∑12PAHs, PHE and FLU being the predominant compounds [START_REF] Birgul | Concentrations, Gas-Particle Partitioning, and Seasonal Variations of Polycyclic Aromatic Hydrocarbons at Four Sites in Turkey[END_REF].

PCBi were present in all samples with the concentration of the ∑PCBi ranging from 0.024 to 0.327 ng m -3 (Table 1 andTable 2). These values are consistent with those found in Northern France in 2002 [START_REF] Blanchard | The Seasonal Fate of PCBs in Ambient Air and Atmospheric Deposition in Northern France[END_REF] but were much lower than those of the Paris area in the 1980s [START_REF] Granier | Behaviour and spatial and temporal variations of polychlorinated biphenyls and lindane in the urban atmosphere of the Paris area, France[END_REF]. Thus, after a significant drop linked to the French regulation since the 1970s, a steady state was observed due to the persistence of diffuse sources. Mean concentrations from high volume sampling in urban/industrial location in Barcelona (Spain), in 2005, were similar to ours: 0.17 ng m -3 [START_REF] Mari | Air concentrations of PCDD/Fs, PCBs and PCNs using active and passive air samplers[END_REF] The order of PCBi abundance was CB52 > CB101 > CB28 > CB153 > CB138 > CB118 > CB180 (Table SM.8). ∑PCB-DL represented only 8 to 12% of the total PCBs. Among the 4 non-ortho substituted congeners, that share a structural similarity and toxic mode of action with polychlorinated dibenzo-p-dioxins, only CB77 and CB81 were detected at a few pg m -3 with a frequency approximately 10%. Both congeners were the most abundant coplanars, and this has been found to be the case in the commercial Aroclor and Clophen mixtures [START_REF] Schulz | Complete characterization of polychlorinated biphenyl congeners in commercial Aroclor and Clophen mixtures by multidimensional gas chromatographyelectron capture detection[END_REF] and in indoor air [START_REF] Kohler | Coplanar polychlorinated biphenyls (PCB) in indoor air[END_REF]. However, toxic effects such as endocrine disruption are also associated with other congeners within the group [START_REF] Caserta | Impact of endocrine disruptor chemicals in gynaecology[END_REF].

The occurrence of PBDEs depends on the congeners considered, and the concentrations were low, from 0.001 to 0.016 ng m -3 as ∑8PBDEs. PBDE concentrations were 10-to 30-fold lower than PCBs. These concentrations are in accordance with total air concentrations found in the Paris centre in 2008-2009 [START_REF] Tlili | Polybrominated diphenyl ether dynamics in ambient air and atmospheric bulk/wet deposition in downtown Paris (France)[END_REF] and in Munich (Germany) in 2008 [START_REF] Fromme | Human exposure to polybrominated diphenyl ethers (PBDE), as evidenced by data from a duplicate diet study, indoor air, house dust, and biomonitoring in Germany[END_REF].

BDE47 was quantified with a frequency up to 100%, whereas BDE209 was detected in only 50% of the samples. A higher LOQ for BDE209 compared to BDE47 could contribute to such results. Two different potential sources of PBDEs were reported in urban ambient air, in Taiwan: the lighter brominated PBDEs were mainly originated from indoor air, while their highly brominated ones were attributed to combustion sources, such as vehicles [START_REF] Wang | Polybrominated diphenyl ethers in various atmospheric environments of Taiwan: Their levels, source identification and influence of combustion sources[END_REF]. . HCB and PeCB were detected in 100% of samples and displayed low concentrations, < 0.06 ng m -3 . HCB production and commercialisation in Europe ceased in 1993, however it is still released into the environment as a by-product or impurity from the manufacture of chlorinated solvents, aromatics and pesticides. The European Chlorinated Solvent Association reported that 4 000 tons of HCB were produced in Europe for 1996, during the manufacture of tetrachlorethylene and that over 99% were incinerated at high temperature [START_REF] Bonnomet | Hexachlorobenzene. Ineris[END_REF]. Another potential source of HCB to the environment is from the bioisomerization of lindane in agricultural soil [START_REF] Waliszewski | Residues of lindane, HCH isomers and HCB in the soil after lindane application[END_REF].

BPA was quantified in 75% of the samples and at low concentrations, ranging from 0.01 to 0.1 ng m -3 . However, these results need to be confirmed because of low recoveries of the deuterated internal standard, owing to the deuterium/hydrogen exchange in hydroxyl groups when BPA-D 16 was dissolved into a protic solvent such as methanol/water [START_REF] Ballesteros-Gomez | Analytical methods for the determination of bisphenol A in food[END_REF].

Spatial trends

Urban centre/suburban area (Paris/Lognes 2011/2012)

Despite the high population density of 20 000 inhabitants per km -2 in the Paris area (urban) versus 4 400 inhabitants per km -2 at Lognes (suburban; 20 km from the sampling site of Paris), differences between ambient air concentrations at the two sampling sites were minor (Table 1).

No differences were observed for PAHs, APs, PBDEs, HCB and PeCB. For PCBi and PAEs, the concentrations were two times lower at the suburban site than at the urban site (p < 0.05).

Thus, PCBs and PAEs showed an urban signature, whereas AP, PBDE and PAH sources were more distributed along the urban-suburban transect. In the Great Lakes basin (USA), PCBs opposite to PAHs showed a strong urban signature [START_REF] Hafner | Potential sources of pesticides, PCBs, and PAHs to the atmosphere of the Great Lakes[END_REF].

For PAHs, the source regions were less distinct as the molecular weight of the compounds increased. Indeed, the PAHs in gaseous phase are more susceptible than those adsorbed on particles to degradation via reaction with OH-radical, ozone and NO X or photolysis. For FLU, PHE, FTH and PYR well known to be emitted from gasoline engine, coal combustion and coke ovens, atmospheric lifetime under OH-reaction varied from 26 h (FLU), to 5.6 h (FHE) and 3-5 h (FLU and PYR) [START_REF] Atkinson | Atmospheric chemistry of gas-phase polycyclic aromatic hydrocarbons: formation of atmospheric mutagens[END_REF]. As a major source of OH-radicals in the atmosphere is the photolysis of ozone [START_REF] Alvarez | Unexpectedly high indoor hydroxyl radical concentrations associated with nitrous acid[END_REF], the degradation potentials were estimated by ozone concentrations at the urban and the suburban site. They remained very similar as no differences were observed in ozone concentrations (Table SM.1).

For APs, wastewater treatment plants, usually located outside urban areas, were identified as a major source to ambient air during water-air exchange processes [START_REF] Salgueiro-González | Analysis and occurrence of endocrine-disrupting chemicals in airborne particles[END_REF].

Population density is a major factor impacting semi-volatile organic compound emissions in urban area as reported in a study in USA that noted indoor sources as the predominant factor influencing outdoor ambient air concentrations in densely populated areas [START_REF] Rudel | Endocrine disrupting chemicals in indoor and outdoor air[END_REF]. Indeed, in a major UK conurbation, the principal contemporary source of PCBs appears to be the ventilation of indoor air [START_REF] Jamshidi | Concentrations and chiral signatures of polychlorinated biphenyls in outdoor and indoor air and soil in a major UK conurbation[END_REF]. Moreover, emissions from indoor air to outdoors for BDE209 and sum of BDE28, 47, 99, and 153, were roughly estimated to represent close to 90% of total emissions to outdoor air in Sweden, indicating that contaminated indoor air is an important source of PBDE contamination [START_REF] Björklund | Indoor Air Is a Significant Source of Tri-decabrominated Diphenyl Ethers to Outdoor Air via Ventilation Systems[END_REF].

However, Lognes is located under prevailing westerly winds (frequency > 25%) passing first over the Paris centre. Thus, recirculation of the contaminated air mass over the urban zone can also impact the contamination level at the suburban site located 20 km far from the urban site and under the air mass plume. Similarly, in the UK, a direct correlation between wind direction and PCB ambient air concentration was observed, in accordance with inputs from winds passing over the Birmingham city centre (3 km away from the sampling site)

because the main source of tri-and tetra-chlorinated congeners is a non-equilibrium, shortrange transport [START_REF] Currado | Factors Influencing Atmospheric Concentrations of Polychlorinated Biphenyls in Birmingham[END_REF].

3.2.2. Urban centre/forest area (Paris/Fontainebleau 2010/2011) Spatial differences of compound concentrations were observed from the urban site to the forest site, 56.5 km apart (p < 0.05) (Table 2), with decreases ranging from 2-to 5-fold, according to the compounds.

Differences were clearly shown for ∑7PAEs (concentration ratio between the urban and the forest site = 5, p < 0.001, Mann-Whitney test) and APs (ratio = 3, p < 0.05) and at a lower magnitude for ∑8PAHs and ∑PCBi (ratio = 2, p < 0.2). In contrast, no differences were observed for ∑8PBDEs, HCB and PeCB, as previously observed for the urban/suburban sites.

Several processes might explain that spatial distribution. First, emissions related to high building density in urban areas might constitute the major source of PAEs and APs to ambient air. Indeed, in California (USA), of all of the chemicals studied in paired indoor and outdoor air samples, most supported the hypothesis of dominant indoor sources except for PAHs, which had a significant outdoor contribution [START_REF] Rudel | Semivolatile endocrine-disrupting compounds in paired indoor and outdoor air in two northern California communities[END_REF]. However, in Stockholm (Sweden) the indoor environment contributes only about 25% of BDE209 to the air pollution load [START_REF] Cousins | Emissions of two phthalate esters and BDE 209 to indoor air and their impact on urban air quality[END_REF] suggesting the existence of additional sources in the outdoor environment.

Less marked variations in concentrations of PCBs and PBDEs between the urban and the forest area were consistent with their persistence far away from their emission sources, with half-lives under photo-degradation conditions ranging from 3 to 120 d for PCBs [START_REF] Bunce | An assessment of the importance of direct solar degradation of some simple chlorinated benzenes and biphenyls in the vapor phase[END_REF] and from 2 to 94 d for PBDEs [START_REF] Wania | Assessing the long-range transport potential of polybrominated diphenyl ethers :a comparaison of four multimedia models[END_REF]. In the Toronto area (Canada), data from PUF passive samplers showed that PBDEs were fairly uniform along an urban-rural transect, in accordance with our observations [START_REF] Harner | Passive sampler derived air concentrations of PBDEs along an urban-rural transect: Spatial and temporal trends[END_REF]. In the same area, 95% of PCB and 70% of PBDE emissions undergo atmospheric transport from the city, the urban air plume reaching about 50 km in the direction of prevailing winds [START_REF] Csiszar | The Magnitude and Spatial Range of Current-Use Urban PCB and PBDE Emissions Estimated Using a Coupled Multimedia and Air Transport Model[END_REF].

Opposite, PAEs and APs were characterised by short half-lives under photodegradation in ambient air, from 5 h to 18 d for PAEs, DEHP being more persistent than low molecular weight PAEs (Staples et al., 1997), and from 10 to 15 h for APs (Neamţu and Frimmel, 2006), leading to a decrease of their ambient air concentrations in the absence of local emission sources, which is documented by the detection of OP in rain and snow [START_REF] Fries | Occurrence of 4-Nonylphenol in rain and snow[END_REF] Concerning PAH concentrations, the small differences found between the 2 sites can be supported by a higher degradation in urban site related to elevate OH-radical, ozone and NO X concentrations compared to the forest site. As a matter of fact, for FLU, PHE and FTH, a major removal mechanism from the gaseous phase by reaction with OH radicals in temperate atmosphere has been reported [START_REF] Halsall | Modelling the behaviour of PAHs during atmospheric transport from the UK to the Arctic[END_REF].

Moreover, we observed an increase spatial homogeneity in winter (1.93 ng m -3 -urban site/1.18 ng m -3 -forest site) compared to summer (0.918 ng m -3 -urban site/0.215 ng m -3forest site) (Table 2). A similar result was observed in Toronto (Canada) as emissions from domestic heating, with a large part played by natural gas (94%) in urban area, corresponded to relatively low PAH emissions, compared to gasoil or wood, and lead to a greater increase in the rural compared to the urban concentrations in winter [START_REF] Melymuk | PCBs, PBDEs, and PAHs in Toronto air: spatial and seasonal trends and implications for contaminant transport[END_REF]. Last, the vicinity of main highways crossing the forest area could contribute to local PAH emissions.

For HCB a steady concentration of approximately 0.05 ng m -3 was found, suggesting that there is no major primary source of HCB in the Paris area. Opposite, a spatial variation of HCB in air from an urban-rural transect across Tianjin (China) was shown, related to unintentionally in course of substantial chlor-alkali production ( [START_REF] Zheng | Spatial and seasonal variations of organochlorine compounds in air on an urban-rural transect across Tianjin, China[END_REF].

Temporal trends

Summer/winter variations

Clear variations for the three sites were observed between summer and winter for PAHs, APs, PAEs and PCBs (Table 1 andTable 2). The most marked difference was found for BaP concentrations, with summer/winter increases up to 14-fold. For the ∑8PAHs, a 2-to 5-fold concentration increase in the winter of 2011 and a 2-fold increase in the winter of 2012 were found. The winter season corresponds to lower degradation processes and to high domestic heating activities, that contributes to explain the summer/winter differences. Photochemical reactions of PAHs may constitute important decay routes for these compounds in the atmosphere [START_REF] Albaigés | Vapor-particle partitioning of hydrocarbons in Western Mediterranean urban and marine atmospheres[END_REF]. A main source of OH-radicals that oxidize compounds in the atmosphere, being the photolysis of ozone [START_REF] Alvarez | Unexpectedly high indoor hydroxyl radical concentrations associated with nitrous acid[END_REF], a 2-to 3-fold decrease of ozone concentration in winter due to the attenuation of solar radiation (Table SM.1) could result to a decrease in PAH photolysis.

In contrast, OP concentrations decreased 4-to 7-fold in the winter, depending on the sites (p < 0.05). NP concentrations showed lower discrepancies than OP, with a 3-to 4-fold decrease in the winter of 2011 and no variations in the winter 2012. NP and OP exhibited seasonal dependence with higher gas-phase concentrations during summer than during fall and early winter in the lower Hudson river estuary (USA), suggesting that temperature is a driving factor for their atmospheric occurrence [START_REF] Van Ry | Atmospheric seasonal trends and environmental fate of alkylphenols in the lower Hudson River estuary[END_REF] The variations of PCB and DEHP concentrations were similar to that of APs, with a 2-to 7-fold decrease in the winter. However, CB52 which represent a low molecular weight PCB displayed maximal decrease whereas CB153, a heavier and less volatile congener, showed minor variation. A highly significant relationship between temperature and partial pressure of PCBs, PBDEs and PAHs was reported in the ambient air of Toronto (Canada), their dominant emissions originated from temperature-controlled processes such as volatilisation from local sources under warm temperatures and condensation/deposition under cold temperature [START_REF] Melymuk | PCBs, PBDEs, and PAHs in Toronto air: spatial and seasonal trends and implications for contaminant transport[END_REF].

PBDE concentrations varied little. The restriction in uses for PBDEs which lead to a decrease in emission sources, coupled to their persistence in the environment could contribute to the background level observed, this result being confirmed by low variation of concentrations along the transect urban/suburban/forest area.

Among the compounds emitted by combustion and industrial processes, only HCB, PeCB and FLU remained steady over the year at the three sites. This is consistent with the lack of a major primary source for HCB and PeCB, whereas FLU has been identified as a good marker of emission from diesel vehicles [START_REF] Fang | Characterization, identification of ambient air and road dust polycyclic aromatic hydrocarbons in central Taiwan[END_REF]) that prevail among road traffic in France and remain constant throughout the year. Moreover, degradation processes by atmospheric reactive species reported inside samplers [START_REF] Menichini | On-filter degradation of particle-bound benzo[a]pyrene by ozone during air sampling: A review of the experimental evidence of an artefact[END_REF][START_REF] Melymuk | Current Challenges in Air Sampling of Semivolatile Organic Contaminants: Sampling Artifacts and Their Influence on Data Comparability[END_REF], even for compounds adsorbed on particles [START_REF] Menichini | On-filter degradation of particle-bound benzo[a]pyrene by ozone during air sampling: A review of the experimental evidence of an artefact[END_REF], can lead to underestimate EDC concentrations in the two phases, particularly for the summer period.

Pollutant phase partitioning

The average distribution in the gaseous phase for the different compounds in summer and winter is shown in Fig. 2. In the summer, the high outdoor temperature (approximately 20 °C) and low PM10 concentrations (< 22 µg m -3 ), in contrast to the winter season with low temperatures (< 6.5 °C) and high PM10 concentrations (up to 38 µg m -3 ) (Table SM1), leads to the prevalence of most compounds in the gaseous phase. Thus, the proportions of the different APs and PCBs compounds in the gaseous phase were always > 50% of the total concentrations and were often up to 100%. Other compounds such as DEHP tended to increase in the particulate phase, up to 80% in the cold season (Table 1 and2). However, in summer, the high proportion of DEHP in gaseous form was more linked to the increase of its gaseous phase concentration (up to 32-fold at the urban area) than to the decrease of its particle phase concentration (2-fold).

Because of their high volatility (vapour pressure, VP, 0.63 Pa at 25 °C for NP) compared to the other EDCs, APs prevailed in the gaseous phase in all seasons. A similar phase distribution was reported at an urban site of Germany, with NP concentrations ranging from 0.15 to 1.0 ng.m -3 in the gaseous phase and from 0.002 to 0.117 ng.m -3 in the particulate phase [START_REF] Berkner | Development and validation of a method for determination of trace levels of alkylphenols and bisphenol A in atmospheric samples[END_REF].

PCBs occurred in the gaseous phase, from 97% for the lower chlorinated congeners to 12%

for the highly chlorinated ones as they display a wide range of VP (from 5.8 to 0.00005 Pa) (Table SM.9). A prevailing occurrence in the gaseous phase associated with a decreasing concentration of the highly chlorinated congeners in winter was reported at an industrial location in North China [START_REF] Li | Seasonal Variation and Gas/Particle Partitioning of PCBs in Air from Central Urban Area of an Industrial Base and Coastal City -Tianjin, China[END_REF].

HCB (VP: 2.3 x 10 -3 Pa) was only detected in the gaseous phase, which confirms previous observations in Ontario (Canada) [START_REF] Lane | Gas-and particle-phase concentrations of. alpha.-hexachlorocyclohexane,. gamma.-hexachlorocyclohexane, and hexachlorobenzene in Ontario air[END_REF].

PBDEs were in the gaseous phase from 34% to 99%. These results are consistent with previous studies that indicated that tri-to hepta-BDEs dominated the gaseous phase, accounting for 77% of the total PBDE levels [START_REF] Tlili | Polybrominated diphenyl ether dynamics in ambient air and atmospheric bulk/wet deposition in downtown Paris (France)[END_REF].

Except for BaP, BaA and BghiP, which are mainly associated with particles, PAHs were predominantly in the gaseous phase (Fig. 2). In summer, the most volatile PAHs (VP from 4.1 Pa to 5.7 x 10 -2 Pa) were found at rates up to 100% in the gaseous phase, whereas CHR was equally distributed in both phases. Compound occurrence in the gaseous phase decreased from summer to winter from 50% to 25% of the total concentration for CHR; whereas, for the most volatile PAHs, the gaseous phase remained the predominant phase. This is in accordance with literature data [START_REF] Terzi | Gas-Particle Partitioning of Polycyclic Aromatic Hydrocarbons in Urban, Adjacent Coastal, and Continental Background Sites of Western Greece[END_REF][START_REF] Ballesteros-Gomez | Analytical methods for the determination of bisphenol A in food[END_REF]. The molecular weight of CHR (Mw 228 g mol -1 ) corresponds to the dividing line for the distribution of PAH compounds preferentially in the gaseous or the particulate phase [START_REF] Lu | Pollution level, phase distribution and health risk of polycyclic aromatic hydrocarbons in indoor air at public places of Hangzhou, China[END_REF].

Direct relationships were found between log Kp of EDCs and log K OA (R 2 = 0.335, p < 0.001) and also between the EDC occurrence in the gaseous phase and their log Vp (R 2 = 0.571, p < 0.001) for the summer period (Fig. 3, Table SM.9). Thus, Vp and K OA are relevant parameters for predicting EDC distribution in ambient air, as reported in previous studies [START_REF] Falconer | Vapor pressures and predicted particle/gas distributions of polychlorinated biphenyl congeners as functions of temperature and ortho-chlorine substitution[END_REF][START_REF] Harner | Octanol Air Partition Coefficient for Describing Particle/Gas Partitioning of Aromatic Compounds in Urban Air[END_REF][START_REF] Paasivirta | Estimation of vapor pressures, solubilities and Henry's law constants of selected persistent organic pollutants as functions of temperature[END_REF].

Other environmental parameters, such as UV index or sunshine duration, size and nature of the particles and hygrometry, might interfere with EDC partitioning in ambient air [START_REF] Cousins | Gas-particle partitioning of organic compounds and its interpretation using relative solubilities[END_REF]. In addition, for FLU, PHE and FTH, a major removal mechanism from the gaseous phase, by reaction with OH radicals, in temperate atmosphere, has been reported, [START_REF] Halsall | Modelling the behaviour of PAHs during atmospheric transport from the UK to the Arctic[END_REF].

Two year variations at the Paris siteimpact of ambient parameters (temperature and PM10)

Annual EDC concentrations in ambient air in the Paris centre (Table 1 andTable 2 1 andTable 2).

To enhance knowledge about the influence of ambient parameters upon EDC variability, a principal component analysis (PCA) was performed at a significance level of 95%. EDC concentrations in the ambient air of the urban area were examined in relation to outdoor temperature and PM10 concentrations. PM10 that are from 2 origins, local and regional, may increase with emissions, thermal inversion phenomenon, low wind speed, and air mass recirculation in continental environments and anti-cyclonic conditions with East/North-East wind direction. Two predominant compounds within each chemical group, one of low molecular weight and one of high molecular weight were considered to perform the PCA analysis. Two clusters were identified corresponding to winter and summer samples (Fig. 4).

The correlation matrix for p < 0.05 (Table 3) showed a direct correlation between temperature and CB52 or CB153, OP and DEP. In the summer of 2011, the ambient temperature reached a higher value than in the summer of 2012, which can favour volatilisation from contaminated sites and materials and contribute to the explanation of higher air concentrations for PAEs, APs and PBDEs in 2011. On the contrary, a positive correlation between BaP and PM10 concentrations and a negative correlation between BaP and temperature were found. This result is a consequence of their high production and emission levels in winter and their tendency to be adsorbed upon particles. High PAH concentrations and high PM10 levels during poor vertical mixing associated with the strong barrier of surface inversions were reported in ambient air from rural residential areas in southern Germany [START_REF] Bari | Particle-phase concentrations of polycyclic aromatic hydrocarbons in ambient air of rural residential areas in southern Germany[END_REF].

Conclusions

This study, considering both the gaseous and particulate phases of ambient air, constitutes a first approach to examine multi-residue contamination of ambient air by 55 EDCs in France and provides useful insights into the growing concern regarding chronic exposure to these compounds. The human exposure to indoor air contamination in France was estimated via indoor air concentration data. But, due to the lack of data for outdoor air concentrations (more especially total and gaseous phase concentrations), most of the studies concerning the particles, it remains difficult to estimate the exposure from outdoor air.

The high volume sampling conditions allowed the quantification of all EDCs except TBBPA. Our findings are consistent with molecular properties, environmental conditions and published literature.

Environmental data about ambient air contamination improves the knowledge of distribution variability that depends on location characteristics (urban, suburban, forest) and mainly on temperature conditions (summer, winter). The general trend for seasonal variations was of lower concentrations in winter for most compounds, except for PAHs and in particular BaP, that depend i) on their lower photochemical reaction linked to the increase in the adsorbed form ii) on the decrease in atmospheric reactive species like ozone and iii) on the increase in combustion processes, during the cold season.

Compound distribution between gaseous and particulate phases depends on compound properties such as log K OA and on particulate aerosol concentrations and ambient air temperature. The EDCs studied are largely distributed in the gaseous phase, which leads to the ubiquity of these SVOCs, even far away from their emission source locations.

Our study highlights priority SVOCs that may be considered for monitoring air quality or for the control of diffuse emission sources. Thus, molecules belonging to the PAE and AP families which are already listed as priority compounds for the protection of aquatic environments (DCE -2000), are both ubiquitous and relatively abundant in the atmosphere. In Europe, PAHs are regulated both in ambient air and emissions. The objective of this regulation is to assess the population exposure to air pollution and to improve air quality.

Therefore, some PAE compounds like DEHP and some APs could be associated with PAH monitoring. PAH compounds detected only in winter and at low levels were not taken in account for the gaseous/particulate phase distribution.

  France district (Airparif) (Fig. Supplementary Material -SM 1). Two sampling campaigns were carried out at the following 3 sampling sites in the Paris region: urban centre residential (population density: 20 000 inhab km -2 ) -Paris 13 th (75013), suburban residential area (population density 4 400 inhab km -2 ) -Lognes (77185 -Seine et Marne) and forest area (population density: 87 inhab km -2 ) -Fontainebleau (77186 -Seine et Marne). The prevailing wind direction was W/NW. Because of logistical constraints, only two sites per year were simultaneously sampled: first, Paris/Fontainebleau (distance between the 2 sites, 56.5 km) and then Paris/Lognes (distance 20 km). The first campaign was carried out for two periods: summer 2010 and winter 2010/2011 at the urban (Paris 13 th ) and the forest (Fontainebleau) sites. The second campaign was carried out in summer 2011 and winter 2011/2012 and was performed at the urban and the suburban sites i.e., Paris and Lognes. Each sampling period consisted of three successive and individual samples over 14 d, accounting for 42 sampling days. Sampling conditions are presented in Table SM.1. Air sample volumes ranged from 276 to 555 m 3 .

  . PAHs are expressed as the individual compounds of the French regulation (Decree of 02/02/1998) for atmospheric emissions (ATEP9870017A, 1998): fluorene (FLU), phenanthrene (PHE) and benzo(a)pyrene (BaP), ∑8PAHs (the sum of fluoranthene -FTH, benzo(a)anthracene -BaA, benzo(b)fluoranthene -

Fig. 1 :

 1 Fig. 1: Concentrations as ng m -3 (mean ± SD, n = 3) of EDCs at Paris, Lognes and

Fig. 2 :

 2 Fig. 2: Compound distribution in the gaseous phase as % of total (mean ± SD, n = 9), at the

Fig. 3 :

 3 Fig. 3: Log Kp against log K OA (at 25 °C) and compound as % gaseous phase against log Vp

Fig. 4 :

 4 Fig. 4: PCA projections of the 12 air samples corresponding to the two sampling campaigns at

Fig

  Fig. SM.1: Location of the sampling sites of Airparif (1: urban site -Paris 13th; 2: suburban site -Lognes; 3: forest site -Fontainebleau),

Table 1 :

 1 Concentrations of different EDCs as annual concentrations in total air (mean ± SD), 730 as seasonal concentrations in the gaseous, the particulate phases and the total air (ng m -3 ) and 731 as gaseous (% of total air) at Paris and at Lognes, during summer 2011 and winter 2011-2012.

	732
		Annual
		concentration		Summer 2011 (n=3)			Winter 2011-2012 (n=3)
		(n=6)
	compound	Total (ng m -3 )	Gaseous (ng m -3 )	Particulate (ng m -3 )	% gaseous	Total (ng m -3 )	Gaseous (ng/m 3 )	Particulate (ng m -3 )	% gaseous	Total (ng m -3 )
						Paris
	OP	0.142 ± 0.105	0.191	0.034	85	0.225 ± 0.082	0.056	0.004		0.060 ± 0.019
	NP	0.468 ± 0.140	0.287	0.084	77	0.371 ± 0.108	0.541	0.023		0.564 ± 0.095
	∑OP+NP	0.610 ± 0.118	0.478	0.118	80	0.596 ± 0.155	0.597	0.027		0.624 ± 0.101
	BPA	0.05 ± 0.05	0.076	<LOQ	100	0.076	0.039	0.032		0.071 ± 0.057
	TBBPA		<LOQ	<LOQ	-	-	0.010	0.001		0.013 ± 0.022
	FLU	1.09 ± 0.60	1.16	0.001	100	1.16 ± 0.33	1.00	0.018		1.02 ± 0.871
	PHE	2.57 ± 1.48	2.35	0.016	99	2.37 ± 0.56	2.52	0.26		2.80 ± 2.20
	BaP	0.07 ± 0.08	0.006	0.003	38	0.009 ± 0.003	0.002	0.125	1	0.127 ± 0.084
	∑8PAHs	1.05 ± 0.61	0.470	0.185	72	0.655 ± 0.107	0.512	0.930		1.44 ± 0.666
	HCB	0.054 ± 0.027	0.068	<LOQ	100	0.068 ± 0.03	0.046	<LOQ	100	0.046 ± 0.016
	PeCB	0.018 ± 0.009	0.019	<LOQ	99	0.019 ± 0.008	0.022	<LOQ	100	0.022 ± 0.008
	CB52	0.047 ± 0.022	0.059	<LOQ	100	0.059 ± 0.025	0.034	<LOQ	100	0.035 ± 0.014
	CB153	0.012 ± 0.005	0.015	0.001	84	0.016 ± 0.004	0.007	0.001		0.008 ± 0.002
	∑PCBi	0.129 ± 0.063	0.169	0.005	84	0.170 ± 0.068	0.084	0.005		0.089 ± 0.021
	∑PCB-DL	0.016 ± 0.007	0.021	0.005	94	0.021 ± 0.006	0.011	0.001		0.012 ± 0.002
	DEP	6.99 ± 1.55	6.69	0.436	94	7.13 ± 0.55	4.81	2.05		6.86 ± 2.37
	DiBP	7.85 ± 1.60	7.30	0.330	96	7.63 ± 2.21	8.07	<LOQ	100	8.07 ± 1.15
	DnBP	2.10 ± 0.88	2.66	0.156	94	2.81 ± 0.65	1.39	<LOQ	100	1.39 ± 0.093
	DEHP	25.1 ± 11.4	21.8	8.9	71	30.7 ± 14.7	3.62	15.8		19.5 ± 4.0
	∑7Phthalates	36.3 ± 17.1	40.2	10.0	80	50.2 ± 12.2	18.1	4.2		22.4 ± 3.4
	BDE47	0.0022 ± 0.0019	0.001	0.0001	83	0.001	0.001	0.003		0.004 ± 0.003
	BDE209		<LOQ	<LOQ		-	<LOQ	<LOQ	-	-
	∑8PBDEs	0.0043 ± 0.0051	0.0011	0.0003	77 0.0015 ± 0.0004	0.0009	0.006		0.007 ± 0.006
						Lognes
	OP	0.94 ± 0.066	0.129	0.025	84	0.154 ± 0.015	0.030	0.004		0.034 ± 0.015
	4-NP	0.38 ± 0.12	0.354	0.035	90	0.389 ± 0.053	0.314	0.059		0.373 ± 0.246
	∑OP+NP	0.48 ± 0.17	0.483	0.060	89	0.543 ± 0.052	0.344	0.063		0.407 ± 0.256
	BPA		0.084	<LOQ	100	0.084	<LOQ	<LOQ
	TBBPA		<LOQ	<LOQ	-	-	0.008	<LOQ		0.008 ± 0.01
	FLU	0.84 ± 0.36	0.853	0.001	100	0.853 ± 0.113	0.814	0.014		0.828 ± 0.012
	PHE	1.9 ± 0.96	1.56	0.024	99	1.58 ± 0.224	2.000	0.194		2.19 ± 1.81
	BaP	0.067 ± 0.075	0.008	0.001	89	0.009 ± 0.003	0.002	0.123	1	0.124 ± 0.111
	∑8PAHs	0.90 ± 0.57	0.283	0.322	47	0.604 ± 0.477	0.368	0.818		1.19 ± 0.87
	HCB	0.053 ± 0.021	0.055	<LOQ	100	0.055 ± 0.005	0.033	<LOQ	100	0.033 ± 0.007
	PeCB	0.016 ± 0.0038	0.014	<LOQ	100	0.014 ± 0.001	0.017	<LOQ	100	0.018 ± 0.001
	CB52	0.022 ± 0.010	0.029	<LOQ	100	0.029 ± 0.007	0.014	<LOQ	100	0.014 ± 0.008
	CB153	0.006 ± 0.003	0.007	0.0002	98	0.008 ± 0.001	0.003	0.0007		0.004 ± 0.001
	∑PCBi	0.059 ± 0.026	0.077	0.001	99	0.079 ± 0.017	0.034	0.005		0.039 ± 0.015
	∑PCB-DL	0.006 ± 0.003	0.008	0.001	93	0.009 ± 0.001	0.004	0.0002		0.004 ± 0.002
	DEP	3.78 ± 1.81	5.99	0.436	99	6.03 ± 1.09	2.52	0.50		3.02 ± 0.48
	DiBP	3.56 ± 2.39	6.42	0.330	97	6.60 ± 0.99	2.29	0.255		2.54 ± 0.97
	DnBP	1.20 ± 1.10	2.45	0.156	95	2.57 ± 0.96	0.742	<LOQ	100	0.742 ± 0.446
	DEHP	12.8 ± 15.7	21.3	1.20	95	22.5 ± 17.9	1.41	1.75		3.16 ± 3.7
	∑7Phthalates	24.1 ± 20.4	37.7	1.57	96	39.3 ± 18.6	7.16	1.81		8.97 ± 0.47
	BDE47	0.001 ± 0.0003	0.001	0.0005	92	0.001	0.0002	0.00055		0.0008 ± 0.0003
	BDE209		<LOQ	<LOQ			<LOQ	<LOQ	-
	∑8PBDEs	0.0014 ± 0.0006	0.0011	0.0006	82	0.001	0.0004	0.0013		0.002 ± 0.002

<LOQ: below the limit of quantification 733

Table 2 :

 2 Concentrations of different EDCs as annual concentrations in total air (mean ± SD), 734 as seasonal concentrations in the gaseous, the particulate phases and the total air (ng m -3 ) and 735 as gaseous (% of total air) at Paris and at Fontainebleau, during summer 2010 and winter

	736
	737	2010-2011.
			Annual		Summer 2010		Winter 2010-2011
			concentration (n=6)			(n=3)			(n=3)
		compound	Total (ng m -3 )	Gaseous (ng m -3 )	Particulate (ng m -3 )	Gaseous (%)	Total (ng m -3 )	Gaseous (ng/m 3 )	Particulate (ng m -3 )	Gaseous (%)	Total (ng m -3 )
							Paris
		OP	0.38 ± 0.38	0.625	0.032	95	0.657 ± 0.379 0.094	0.014		0.11 ± 0.024
		NP	1.14 ± 0.45	1.98	0.099	95	2.08 ± 1.15	0.392	0.094		0.49 ± 0.21
		∑OP+NP	1.66 ± 1.49	2.60	0.131	95	2.74 ± 1.44	0.49	0.11		0.59 ± 0.23
		BPA	0.048 ± 0.053	0.073	0.017	81	0.089 ± 0.047 0.011	<LOQ	100	0.011
		TBBPA		<LOQ	<LOQ			<LOQ	<LOQ
		FLU	1.8 ± 0.7	1.72	<LOQ	100	1.72 ± 0.79	1.88	<LOQ	100	1.88 ± 4.08
		PHE	5.4 ± 1.2	5.01	0.003	99	5.01 ± 1.02	5.76	0.089		5.85 ± 1.46
		BaP	0.07 ± 0.07	0.005	0.018	23	0.023± 0.009	0.019	0.102		0.121 ± 0.083
		∑8PAHs	1.4 ± 0.7	0.897	0.051	95	0.948 ± 0.304	1.22	0.71		1.93 ± 0.62
		HCB	0.054 ± 0.022	0.066	0.001	99	0.067 ± 0.027 0.042	<LOQ	100	0.042 ± 0.009
		PeCB	0.017 ± 0.005	0.015	<LOQ	97	0.016 ± 0.008 0.019	<LOQ	100	0.019 ± 0.002
		CB52	0.065 ± 0.047	0.091	0.012	88	0.103 ± 0.033 0.027	0.002		0.029 ± 0.016
		CB153	0.023 ± 0.007	0.026	0.018	59	0.044 ± 0.023 0.023	0.007		0.03 ± 0.02
		∑PCBi	0.19 ± 0.16	0.267	0.060	82	0.327 ± 0.091 0.055	0.002		0.057 ± 0.033
		∑PCB-DL	0.020 ± 0.025	0.032	0.002	94	0.034 ± 0.032 0.006	0.001		0.007 ± 0.004
		DEP	1.85 ± 2.32	3.67	<LOQ	100	3.67 ± 1.90	<LOQ	<LOQ		<LOQ
		DiBP	15.0 ± 11.9	24.7	0.211	99	24.9 ± 7.17	5.05	0.128		5.19 ± 4.17
		DnBP	4.49 ± 5.08	8.3	<LOQ	100	8.31 ± 4.54	0.671	<LOQ	100	0.671 ± 0.523
		DEHP	60.3 ± 71.3	58.7	3.8	93	62.6 ± 75.8	1.8	7.7		9.5 ± 4.4
		∑7Phthalates	83.3 ± 91.0	151	14.9	90	165 ± 91.6	7.55	8.1		15.7 ± 9.2
		BDE47	0.001	0.001	<LOQ	100		<LOQ	<LOQ		0.02 ± 0.01
		BDE209	0.007 ± 0.003	0.007	0.002	75	0.009 ± 0.004 0.004	0.002		0.006 ± 0.001
		∑8PBDEs	0.0098 ± 0.0011	0.013	0.002	85	0.016 ± 0.003 0.004	0.001		0.005 ± 0.001
						Fontainebleau
		OP	0.15 ± 0.14	0.238	0.029	89	0.267 ± 0.087 0.033	0.004		0.037 ± 0.023
		NP	0.45 ± 0.27	0.626	0.065	91	0.691 ± 0.03	0.162	0.054		0.216 ± 0.157
		∑OP+NP	0.60 ± 0.41	0.864	0.094	90	0.957 ± 0.109 0.195	0.058		0.253 ± 0.179
		BPA	0.116	0.116	<LOQ	100	0.116	0.015	<LOQ	100	0.015
		TBBPA		<LOQ	<LOQ			<LOQ	<LOQ
		FLU	1.3 ± 0.42	1.22	<LOQ	100	1.22 ± 0.51	1.41	<LOQ	100	1.41 ± 0.39
		PHE	2.6 ± 1.2	1.65	<LOQ	100	1.65 ± 0.44	3.432	0.050		3.48 ± 1.02
		BaP	0.050 ± 0.037	0.004	0.005	48	0.009 ± 0.008 <LOQ	0.073	0	0.073 ± 0.026
		∑8PAHs	0.70 ± 0.57	0.200	0.015	93	0.215 ± 0.024 0.646	0.531		1.18 ± 0.33
		HCB	0.048 ± 0.015	0.053	0.001	99	0.054 ± 0.014 0.042	<LOQ	100	0.042 ± 0.016
		PeCB	0.015 ± 0.006	0.012	<LOQ	98	0.013 ± 0.007 0.018	<LOQ	100	0.018 ± 0.006
		CB52	0.026 ± 0.023	0.053	0.009	85	0.062 ± 0.009 0.019	0.002		0.021 ± 0.017
		CB153	0.017 ±0.012	0.010	0.013	43	0.023 ± 0.008 0.009	0.002		0.011 ± 0.005
		∑PCBi	0.10 ± 0.09	0.134	0.045	75	0.180 ± 0.031 0.021	0.004		0.024 ± 0.013
		∑PCB-DL	0.0068 ± 0.0059	0.007	0.004	62	0.012 ± 0.004 0.001	0.001		0.002 ± 0.002
		DEP	0.78 ± 0.92	1.51	<LOQ	100	1.51 ± 0.721	<LOQ	<LOQ
		DiBP	4.02 ± 2.50	5.83	<LOQ	100	5.83 ± 2.30	1.53	0.695		2.21 ± 0.80
		DnBP	1.20 ± 1.07	1.99	<LOQ	100	1.99 ± 0.99	0.367	0.061		0.416 ± 0.273
		DEHP	10.9 ± 14.4	17.8	<LOQ	100	17.8 ± 19.3	1.32	2.72		4.0 ± 2.5
		∑7Phthalates	17.3 ± 18.3	27.7	0.02	99.7	27.9 ± 22.4	3.24	3.56		6.8 ± 2.8
		BDE47	0.0006 ± 0.0005	0.001	<LOQ	100	0.001 ± 0.001 0.000	<LOQ		<LOQ
		BDE209	0.0088 ± 0.0048	0.006	0.003	66	0.010 ± 0.004 0.007	0.001		0.008 ± 0.006
		∑8PBDEs	0.0103 ± 0.0065	0.009	0.004	70	0.012 ± 0.004 0.007	<LOQ		0.008 ± 0.006
	738	<LOQ: below the limit of quantification
	739

Table 3 :

 3 Spearman'r coefficient between air temperature, PM10 and EDC ambient air concentrations at Paris (bold: significant r values for p<0.05, n=14).

		T°C PM10 CB52 CB153 HCB PeCB DEP DEHP BDE47 BDE100 FLU	BaP	OP NP
	PM10	-0.585	1
	CB52	0.720 -0.472	1
	CB153	0.832 -0.574 0.832	1
	HCB	0.692 -0.373 0.462 0.573	1
	PeCB	0.070 0.278 -0.294 -0.196 0.259	1
	DEP	0.606 -0.691 0.613 0.620 0.577 -0.437	1
	DEHP	0.538 -0.521 0.636 0.832 0.315 -0.538 0.472	1
	BDE47 -0.182 0.028 0.238 0.126 -0.259 0.084 -0.282 0.091	1
	BDE100 0.049 -0.201 0.594 0.413 -0.112 -0.378 0.077 0.434	0.573	1
	FLU	-0.154 0.225 -0.364 -0.280 -0.147 0.329 -0.148 -0.336 -0.252	-0.420	1
	BaP	-0.825 0.803 -0.490 -0.706 -0.517 0.105 -0.577 -0.587	0.091	0.028 0.350	1
	OP	0.839 -0.592 0.762 0.762 0.629 -0.252 0.859 0.531 -0.357	0.091 -0.042 -0.615	1
	NP	0.266 0.067 0.434 0.469 0.322 0.049 0.225 0.259 -0.077	0.350 0.133 0.126 0.469 1

Table SM .

 SM 1: Sampling conditions for two campaigns at the urban (Paris), the suburban (Lognes) and the forest (Fontainebleau) sites.TableSM.5: Specifications for the GC/MS analysis. Table SM.6: Calibration ranges, correlations of the linear responses and quantities of native compounds for the spiked matrices.

	747 753 756	Table SM.3: Specifications for the LC-MS/MS analyses Table SM.4: Specifications for the GC-MS/MS analyses (Q: transition for quantification; q:
	754 748 757	Season Summer 2010 Winter 2010/2011 Compound BAP TBBPA transition for qualification). Sunshine duration (hours) 06/01 -06/16/10 Period 06/16 -06/30/10 06/30 -07/13/10 195 01/06 -01/20/11 01/20 -02/02/11 02/02 -02/16/11 Chromatography Apparatus Sites Paris Fontainebleau Paris LCMSMS-ESI Agilent LC (SL serie 1200) triple Quad (G6410 BA) Compounds Internal standards m/z ion quantification m/z ion qualification Ozone µg m -3 65.7 ± 36.9 70.4 ± 34.4 23.5 ± 17.9 Injector Standard: 10 µL Acenaphtylene Phenanthrene d10 152 151 Alkylphenols LCMSMS-ESI AQUITY UPLC®/TQD (Waters). Standard: 10 µL (2.1 mm X 100 mm; 1.7 μm; Air sample volume (m 3 ) (mean±SD) (mean±SD) Air flow (m 3 h -1 ) 276 ± 135 1.4 ± 0.3 357 ± 13 1.3 ± 0.1 331 ± 79 1.2 ± 0.3 Column Others Zorbax Eclipse XDB-C18 Methanol/water Gradient: 40/60 at 0 min then 100/0 from 0 to 10 min, Air temperature (°C) PM10 concentrations Airparif (µg m -3 ) Cumulative precipitation (mm) 20.9 ± 3.1 22.2 ± 3.2 90.3 19.2 ± 2.7 18.0 ± 0.9 95.6 6.3 ± 3.4 28.7 ± 9.6 Mobile phase Flow 0.5 (4.6 X 50 mm; 1.8 µm; Agilent). Chauffée à 50°C. 100/0 from 10 to 12 min and 40/60 from 12 to 17 min. mL/min AQUITY UPLC/BEH C18 Water). Chauffée à 40°C. Methanol and water with ammonium hydroxyde 0,05% Gradient:50/50 at 0 min then 95/5 from 0 to 3 min, 100/0 from 3 to 5 min and 50/50 from 5 to 8 min. 0.4 mL/min EDs Compounds Internal standard RT(min) Source m/z precursor ion Fragmentor (V) m/z quantification m/z qualification Collision Family Compounds Internal standard m/z precursor m/z product Dwell Time (ms) Ec Others PeCB CB30 250 215 Q 50 250 142 q 50 HCB CB30 249 214 Q Acenaphtene Phenanthrene d10 153 154 Fluorene Phenanthrene d10 166 Compounds Calibration ranges (pg) r 2 Quantity (ng) 165 Phenanthrene Phenanthrene d10 178 BPA 2-20000 > 0.997 50 179 Anthracene Phenanthrene d10 178 179 TBBPA 2-20000 > 0.999 50 50 284 249 q 50 Fluoranthene Pyrene d10 202 200 PAHs 10-1000 > 0.996 100 43.4 36 Fontainebleau 44.8 ± 18.7 401 ± 7 1.4 ± 0.1 4.7 ± 3.3 24.5 ± 9.2 50.4 Summer 2011 05/30 -06/14/11 06/14 -06/28/11 06/28 -07/12/11 Paris 57.9 ± 29.5 499 ± 82 1.7 ± 0.2 19.2 ± 1.0 19.3 ± 2.3 86.2 158 Lognes 61.8 ± 32.5 555 ± 59 1.9 ± 0.1 18.4 ± 1.0 16.8 ± 1.7 98.9 Winter 2011/2012 01/24 -02/08/12 02/08 -02/21/12 02/21 -03/06/12 Paris 19.8 ± 16.5 454 ± 38 1.5 ± 0.1 4.0 ± 4.1 37.9 ± 4.8 19.4 107 Lognes 24.7 ± 18.5 475 ± 98 1.6 ± 0.2 3.0 ± 4.3 32.7 ± 1.8 27.4 ion fils Ce(eV) ion fils Ce (eV) Alkylphenols OP n-NP 3.25 ESI negatif ; N2: 380°C ; gas flow: 800 L/h; Capillaire: 2800 V 205 45 134.2 17 133.2 30 Ar (0.25 mL/min) NP n-NP 3.52 219 40 133.2 26 147.2 26 Phenols BPA BPA-d16 5.35 ESI negatif ; N2: 350°C ; gas flow: 660 L/h; Capillaire: 4000 V 227.1 125 212.1 12 133.1 20 N2 TBBPA 13 C12-TBBPA 9.3 543 130 81 60 417.8 40 Ethyl-P 4.1 165.1 110 92 20 137 8 Propyl-P 5.4 179.1 80 92 24 136 12 Butyl-P 6.5 193.1 110 92 20 136 12 RT: Retention Time; Ce: Collision energy; ESI: Electro Spray Ionization PCBs Source: 300 °C Interface: 250 °C Quadrupoles: 150 °C Tri CB30 256 186 Q 50 256 151 q 50 Tetra CB30 292 222 Q Pyrene Pyrene d10 202 200 HCB 0.8-800 > 0.999 100 Source: 230 °C Benzo(a)anthracene Benzo(a)anthracene d12 228 226 PeCB 0.8-800 > 0.999 100 25 292 220 q 25 Penta CB107 326 256 Q 25 326 254 q 25 Hexa CB107 360 290 Q Interface: 250 °C Quadrupoles: 150 ° C Chrysene Benzo(a)anthracene d12 228 226 Benzo(b)fluoranthene Benzo(a)anthracene d12 252 PCBs 0.8-800 > 0.999 50 253 Benzo(k)fluoranthene Benzo(a)anthracene d12 252 PAEs 31.25-8000 > 0.998 2000 253 Benzo(a)pyrene Benzo(a)anthracene d12 252 PBDEs 35-476 > 0.999 25 253 25 360 325 q Hepta CB107 394 324 Q 394 359 q 13C12 PCB 194 Syringe standard 442 370 Q 440 370 q PBDEs BDE28 13C BDE47 407.8 247.9 Q Source: 275 °C BDE209 13C BDE209 799.7 640 Q 75 Interface: 250 °C 247.9 139 q BDE47 13C BDE47 485.7 325.9 Q 325.9 138 q BDE100 13C BDE47 403.7 137 Q 565.7 405.9 q BDE99 13C BDE47 403.7 137 Q 565.7 405.9 q BDE154 13C BDE153 643.6 483.9 Q 483.9 376.8 q BDE153 13C BDE153 643.6 483.9 Q 483.9 376.8 q BDE183 BDE181 561.6 454.6 Q 721.6 561.6 q 75 75 Benzyl benzoate Syringe standard 105 212 75 DPP 149 104 75 DiDP DPP 307 149 75 Quadrupoles: 150 °C DiNP DPP 293 149 75 DnOP DPP 149 279 75 Interface: 200 °C DEHP DPP 149 279 75 BBP DPP 149 104 75 Source: 230 °C DnBP DPP 149 223 75 DiBP DPP 149 104 80 DEP DPP 149 177 80 DMP DPP 163 194 90 Benzyl benzoate Syringe standard 105 212 90 Benzo(a)anthracene d12 240 236 60 Pyrene d10 212 213 60 Phenanthrene d10 188 189 60 Benzo(g,h,i)perylene Benzo(a)anthracene d12 276 274 60 Dibenzo(a,h)anthracene Benzo(a)anthracene d12 278 276 25 Indeno(1,2,3-cd)pyrene Benzo(a)anthracene d12 276 274 BDE209 350-4760 > 0.998 250
		13C12 BDE47	IS	797.7 497.7	637.7 q 337.9 Q	75 80	Quadrupoles: 150 °C
				337.9	148.9 q	80
		13C12 BDE153	IS	655.7	495.8 Q	75
				495.7	335.8 q	75
		BDE181	IS	561.6	454.6 Q	75
				721.6	561.6 q	75
		13C12 BDE209	IS	811.4	651.4 Q	75
				809.4	649.5 q	75
		BB209	IS	943.5	783.7 Q	70
				783.7	625.7 q	70
		CB209	IS	499.7	427.9 Q	75
				427.9	357.8 q	75
	755

Table SM .

 SM 7: Instrument detection limits (IDLs -pg on column for the low standard 761 solutions, as the concentration with a signal/noise ratio of 3 peak to peak), limits of 762 quantification (LOQs -pg m -3 ), recoveries (as % in spiked XAD-2 and filter matrices) and 763 average blanks (pg m -3 ) for gaseous and particulate phases. For LOQs and recoveries, XAD-2 764 resin and quartz filters were spiked, before extraction, with all native compounds. After 765 extraction, the ISs were added and the extract followed the entire procedure. The LOQ was TableSM.8: Annual compound concentrations as mean ± SD (n = 6) and median for the 770 phthalates as compounds and ∑7PAEs, for the PAHs as compounds, ∑8PAHs (bold) and 771 ∑15PAHs and for the PCBs as compounds, ∑PCBi (bold), ∑PCB-DL (italic) and ∑19PCBs.TableSM.9: EDC vapor pressure (Pa, at 25 °C), log K OA (at 25 °C), EDC distribution (as % of total concentration) in gaseous phase of the ambient air and Kp, considering the mean of the three sites during summer (mean temperature 20 °C) and winter (mean temperature 4.5 °C).

	772
	766
	767	considered as the concentration (in pg m -3 ) with a signal/noise ratio of 9 (peak to peak). Fontainebleau (2010-2011) Lognes (2011-2012) Paris (2010-2011)	Paris (2011-2012)
	768 Family DMP DEP PBDEs DiBP DnBP BBP DEHP DnOP ∑7PAEs Acenaphtylene Acenaphtene Fluorene Phenanthrene Indicators Anthracene Fluoranthene Pyrene Benzo(a)anthracene Chrysene Benzo(b)fluoranthene Benzo(k)fluoranthene	Compounds Mean 0.03 0.76 BDE28 4.03 BDE47 1.20 BDE100 0.02 BDE99 BDE154 BDE153 BDE183 BDE209 10.9 0.31 17.3 0.001 0.539 PeCB 1.32 HCB 2.57 CB28 0.002 CB52 CB101 CB118 CB138 0.453 0.260 0.032 0.076 CB153 0.083 0.002	IDLs (pg on column) Median 0.04 SD 0.01 Compound Vapor pressure Log KOA LOQ Gaseous phase LOQ Particulate phase Mean SD Median 0.41 0.30 0.43 % in gaseous phase Recovery Gaseous phase Mean 0.11 0.95 0.39 4.53 1.81 4.30 1.84 Pa at 25°C at 25°C Summer Winter 0.30 0.2 1.0 87 2.51 3.31 4.58 2.39 4.34 15.0 OP 6.27E-01 9.24 88.2 87.1 0.24 0.6 4.1 98 1.08 0.95 1.66 1.20 1.51 4.49 NP 6.00E-01 8.62 88.2 80.6 0.66 0.6 1.6 102 0.02 0.01 0.24 0.19 0.25 0.15 CB28 5.81E+00 8.35 94.5 95.6 0.51 0.6 1.6 107 2.04 1.5 0.8 92 1.41 1.8 1.0 100 1.35 1.7 14.9 103 7.5 9.9 79.1 98 14.4 5.07 12.8 15.7 4.63 60.2 0.62 0.07 0.29 0.26 0.32 0.08 CB52 3.30E+00 8.68 93.2 97.1 18.3 8.55 24.13 20.4 13.7 83.3 CB101 5.55E-01 9.45 93.1 97 0.002 0.265 0.425 0.004 0.225 CB105 8.67E-04 9.88 91.8 91.3 0.335 0.405 0.403 0.337 0.490 0.787 CB110 9.50E-04 9.45 90 93 0.1 0.2 0.3 50 0.417 1.48 0.840 0.461 0.903 1.80 CB118 1.75E-01 9.88 91.5 94.4 0.12 0.3 0.6 57 1.23 2.48 1.89 1.20 1.65 5.43 CB138 6.85E-02 10.21 68 75.2 0.03 0.9 0.4 90 0.002 0.001 0.032 0.051 0.003 0.002 CB153 9.11E-02 10.21 71 80 0.09 0.2 0.1 93 0.1 1.1 0.2 96 0.09 0.4 0.3 125 0.27 0.4 0.5 124 0.322 0.386 0.616 0.432 0.469 1.04 0.216 0.250 0.316 0.289 0.177 1.02 CB156 2.10E-04 10.65 83.2 67.7 0.037 0.020 0.074 0.105 0.027 0.076 CB157 2.10E-04 10.65 71.8 70.9 0.084 0.050 0.120 0.142 0.067 0.130 CB169 6.31E-05 11.08 80.3 69.5 0.16 0.1 0.2 109 0.098 0.056 0.082 0.119 0.027 0.115 CB180 1.73E-04 10.98 81.3 52.2 0.005 0.000 0.001 0.003 0.000 0.001 CB189 5.01E-05 11.41 72.9 12.1	Recovery Particulte phase SD 0.13 Kp 2.35 Summer 95 12.0 1.71E-01 2.10E-01 Average blanks Gaseous phase (pg m -3 ) Median Mean 0.08 0.46 0.74 6.99 Winter 12.4 7.85 0.2 94 5.09 2.22 2.10 1.85E-01 2.43E-01 0.8 < LOQ 0.22 0.01 0.33 6.01E-02 7.12E-02 86 88 < LOQ 89 < LOQ 94 < LOQ 89 < LOQ 93 < LOQ 71.3 21.6 25.1 0.09 0.03 0.30 7.99E-02 3.95E-02 91.0 39.0 36.3 8.39E-02 3.64E-02 0.549 0.175 1.03E-01 1.13E-01 0.620 0.687 0.642 9.28E-02 1.02E-01 61 1.6 0.694 1.64 1.09 1.02E-01 6.96E-02 62 2.0 1.220 5.56 2.57 1.01E+00 6.53E-01 95 4.1 0.003 0.001 0.034 6.92E-01 1.25E-01 100 17.7 101 8.6 115 4.3 107 18.0 0.310 1.01 0.747 0.675 0.880 0.450 2.70E-01 2.37E+00 0.072 0.073 0.082 4.78E-01 2.64E-01 0.107 0.136 0.145 2.65E-01 3.03E-02 109 17.4 0.158 0.056 0.109 2.60E-01 3.30E+00 0.003 1.12E+00 1.76E+00	Average blanks Particulate phase SD Median 0.29 0.41 1.55 7.39 (pg m -3 ) 1.60 7.73 < LOQ 0.89 1.95 < LOQ 0.33 0.28 < LOQ < LOQ < LOQ < LOQ 11.5 21.30 0.33 0.26 17.2 31.3 0.422 0.003 0.419 0.571 < LOQ 0.596 1.35 0.37 1.48 2.66 < LOQ 0.052 0.004 2.7 11.9 5.2 2.9 0.381 0.674 0.332 0.282 0.097 0.043 0.165 0.082 22.3 0.135 0.051 22.8 0.005 0.000
	PCBs Benzo(a)pyrene DL Indeno(1,2,3,c,d)pyrene Dibenzo(a,h)anthracene Benzo(g,h,i)perylene ∑8PAHs ∑15PAHs	CB180 CB77 0.041 CB81 0.004 CB126 CB169 CB105 < LOQ 0.081 0.696 5.46	0.039 HCB 0.006 PeCB 0.086 BPA 0.567 DMP 2.228 DEP	0.11 0.05 0.030 0.06 0.18 0.07 0.09 0.059 0.543 5.195	0.2 0.6 0.067 3.07E-01 0.3 < LOQ 2.67E+02 0.6 0.2 0.4 < LOQ 0.056 5.33E-05 0.895 2.63E-01 4.761 1.47E-01	0.094 7.64 6.46 0.080 12.70 0.705 7.01 3.08 7.55	0.4 0.8 0.4 0.3 0.3 2.4	0.022 99.3 99.7 0.017 95.2 0.685 89.7 4.22 98.2	133 98 0.072 99.7 102 0.007 98.4 127 136 113 < LOQ 0.13 85 1.44 77.8 10.834 79.2	109 96 0.075 7.50E-03 2.70E-03 0.047 101 0.011 < LOQ 1.70E-02 2.70E-03 112 113 111 0.137 0.096 4.20E-02 1.38E-01 0.696 1.24 1.56E-01 3.82E-01 2.74 9.98 2.18E-02 1.58E-01	3.3 < LOQ 0.068 < LOQ < LOQ < LOQ < LOQ 1.1 < LOQ 0.040 1.05 6.160	15.2 0.084 < LOQ < LOQ < LOQ < LOQ < LOQ 0.038 0.607 3.21	0.031 0.030 0.852 6.01
		CB28		CB114 0.0121	0.0117 DnBP	0.10 0.0095	0.4 0.0085 4.73E-03	0.0044 8.56	0.3	0.0052 98.1	113 0.0237 81.7	105 0.0199 1.92E-02 6.99E-01 0.0215	< LOQ 0.0131	< LOQ 0.0055	0.0118
		CB52		CB123 0.0364	0.0287 DiBP	0.10 0.0340	0.4 0.0216 4.73E-03	0.0102 8.54	0.3	0.0222 97.4	125 0.065 90.6	103 0.0472 2.82E-02 1.34E-02 0.0623	< LOQ 0.0469	< LOQ 0.0224	0.0422
	CB101 Others CB110 CB81 CB77 CB123 CB118		CB156 0.0257 CB157 CB167 CB189 CB110 0.0156 0.00001 0.00029 0.0001 DMP 0.0034	0.0235 BBP 0.0140 DEHP 0.00021 DnOP 0.0003 BDE28 0.0031 BDE47	0.07 0.0226 0.06 0.07 0.13 0.1 0.0139 0.00022 0.08 0.0032	0.1 0.0123 2.50E-05 0.4 2.2 0.2 2.1 0.0058 0.00003 2.50E-05 0.00013 1.84E-06 0.0001 2.70E-04 50.0 0.0045 3.30E-04	0.0067 8.78 0.0029 10.53 0.00011 10.04 0.0002 9.70 0.0016 10.46	0.3 0.3 1.4 0.5 0.9 6.0	0.0108 92.4 0.0054 89.7 0.00008 58.5 95.9 0.0045 93.7	82 0.0506 88.9 134 135 133 65 0.0330 0.00001 29 0.00033 19.5 0.0018 99.1 91 0.0087 55.3	107 0.0459 1.17E-01 1.93E+00 0.0390 108 106 117 63 0.0294 0.0293 1.08E-01 4.61E+00 0.00023 0.00034 4.22E-01 3.11E+01 0.0024 0.0006 4.93E-02 5.50E-03 78 0.0078 0.0070 8.24E-02 4.88E+00	0.3 0.036 < LOQ < LOQ 0.2 4.9 0.0183 0.00004 0.00040 0.0002 247 0.0111	0.8 < LOQ 0.0271 < LOQ < LOQ 0.0131 0.00048 0.0003 3.1 51 0.0040	0.0267 0.0138 0.00024 0.0106
	CB114		DEP 0.0002	BDE100	0.09	50 0.0003 4.69E-05	11.40	0.7	85.5	90 < LOQ 51.4	83 9.17E-02 1.27E+00	1017 < LOQ	549
	CB153		DiBP 0.0123	0.0121 BDE99	0.09 0.0111	83 0.0058 4.69E-05	0.0026 11.20	5.7	0.0047 50	101 0.0233 34	77 0.0270 1.02E+00 6.38E+00 0.0145	2615 0.0123	2998 0.0051	0.0121
	PAEs CB105		DnBP 0.0011	0.0010 BDE209	0.06 0.0010	69 0.0014 4.60E-06	0.0008 15.73	9.6	0.0014 70	102 0.0027 80	89 0.0023 4.62E-01 3.34E-01 0.0024	1050 0.0040	590 0.0018	0.0036
	PAHs CB138 CB126 CB167 CB156 CB157 CB180 CB169 CB189 BDE153 BDE154 BDE99 BDE100 BDE47 BDE28 ∑PCBi ∑PCB-DL ∑19PCBs	BBP DEHP DnOP Acenaphtylene 0.0100 < LOQ Acenaphtene 0.0099 0.00007 0.00008 Fluorene 0.0002 0.0001 Phenanthrene Acenaphtene 0.00147 0.00357 Fluoranthene Fluorene 0.0019 0.0018 Benzo(a)pyrene 0.90 0.30 0.30 0.27 0.0091 0.00005 0.0002 0.12 0.0001 0.09 0.0013 Phenanthrene 0.18 < LOQ Pyrene Anthracene 0.19 0.00009 0.00011 0.00003 Benzo(a)anthracene Fluoranthene 1.50 Pyrene 1.58 Benzo(a)anthracene 0.63 Chrysène 0.60 Benzo(b)fluoranthene 0.86 Benzo(k)fluoranthene 0.61 Benzo(a)pyrene 2.50 Indeno(1.2.3.c d)pyrene 0.48 <LOQ <LOQ <LOQ <LOQ 0.001 0.001 <LOQ 0.102 0.0878 0.0907 0.0068 0.0059 0.0062 Chrysene 0.121 0.103 0.111 Benzo(g,h,i)perylene	49 92 254 46 0.0040 < LOQ 4.14E+00 0.00006 4.50E-01 0.0001 5.70E-02 9.2 0.00004 5.60E-03 137 0.0024 3.20E-06 2.7 < LOQ 4.10E-03 6.6 0.00004 2.30E-04 8.1 1.0 1.0 0.7 0.7 4.6 4.6 4.5 <LOQ <LOQ 0.001 <LOQ 0.001 <LOQ 0.0589 0.0065 4.80E-05 0.067 1.10E-12	0.0017 0.00005 7.19 0.0002 7.90 0.00004 9.32 0.0026 9.32 9.32 0.00005 0.0259 0.0027 0.030	3.8 2.8 11 1.6 2.1 0.4 2.1 2.1 0.00000 0.0046 100 0.00006 100 0.0001 99.2 0.00004 85.8 0.0011 49.5 95.5 46.6 0.3 0.3 1.8 1.8 0.5 0.5 0.4 0.6 0.0514 0.0065 50.6 0.059 27.1	127 56 63 54 0.0188 < LOQ 100 0.00006 82.9 0.0004 94.8 67 0.00037 67.2 90 0.0022 4.4 76 < LOQ 75.6 67 0.0065 12.2 71 61 53 61 59 67 60 58 0.0002 <LOQ 0.0013 0.0005 0.0017 0.0001 0.192 0.021 25.4 0.237 3.6	98 101 102 47 0.0213 0.00007 4.00E-04 4.70E-03 0.0124 0.00005 0.0003 0.0003 5.00E-03 4.20E-02 50 0.00035 0.00033 2.41E-01 3.33E-01 54 0.0021 0.0018 3.71E-01 4.47E+01 55 4.85E-02 4.45E-01 55 0.0155 0.0004 7.29E-01 1.53E+01 56 55 53 52 51 54 46 45 0.0005 0.0015 0.0006 0.0008 0.0001 0.0019 0.0008 0.160 0.159 0.025 0.011 5.97E-01 1.16E+01 0.198 0.192 2.62E-01 5.66E+01	469 2133 < LOQ < LOQ 0.0079 < LOQ 0.00015 0.0004 < LOQ 0.00039 < LOQ 0.0020 193 < LOQ < LOQ 0.00002 14.7 11.8 < LOQ < LOQ < LOQ < LOQ < LOQ < LOQ <LOQ <LOQ 0.0013 0.0006 0.0023 0.0001 0.129 0.016 0.153	617 2092 970 0.0021 0.00012 0.0003 < LOQ 0.00028 < LOQ 0.0012 < LOQ 16.3 0.00003 0.00000 0.0072 0.00013 0.0003 0.00031 0.0022 < LOQ 11.9 11.6 < LOQ < LOQ 0.0020 0.0002 < LOQ 0.0009 0.0002 < LOQ 0.0022 0.0012 6.8 2.4 0.0634 0.112 0.0067 0.015 0.079 0.131
	BDE183	Dibenzo(a.h)anthracene <LOQ	0.50	1.4 <LOQ		0.5		54 0.0010	45 0.0028		< LOQ <LOQ	< LOQ
	Benzo(g.h.i)perylene BPA 0.0088 0.0048 TBBPA 0.0103 0.0065 < LOQ : under limit of quantification 0.27 4.4 BDE209 Phenols 0.0096 0.48 ∑8PBDEs 0.0103 769 773	2.8 5.4 <LOQ 103 0.0014	0.0006	0.5 18 39	0.0011	87 120 0.0048 12 0.0098	95 22 0.0044 29 0.0120	0.0055 0.0072	< LOQ 300 <LOQ < LOQ 0.0043	1.2 196 0.0051 < LOQ	0.0017

Acknowledgments:

This work was supported by the French Agency for Food, Environmental and Occupational Health & Safety -ANSES, under the frame of the "Programme National de Recherche sur les Perturbateurs Endocriniens" (PNRPE). Financial contributions were given by the Agence de l'Environnement et de la Maîtrise de l'Energie -ADEME (Grant n° C09P072) and the Centre Scientifique et Technique du Bâtiment -CSTB (Grant n° C11641). We are grateful to the Association de Surveillance de la qualité de l'air en Île-de-France -Airparif, for providing data about PM10 and for their assistance in climatic parameter interpretation. Technical assistance throughout this study was given by Catherine Bourges and Annie Desportes.