Exposure to PM2.5 modulate the pro-inflammatory and interferon responses against influenza virus infection in a human 3D bronchial epithelium model.

Epidemiological studies showed a positive association between exposure to PM2.5 and the severity of influenza virus infection. However, the mechanisms by which PM2.5 can disrupt antiviral defence are still unclear. From this perspective, the objective of this study was to evaluate the effects of PM2.5 on antiviral signalling in the respiratory epithelium using the bronchial Calu-3 cell line grown at the air-liquid interface. Pre-exposure to PM2.5 before infection with the influenza virus was investigated, as well as a co-exposure. Although a physical interaction between the virus and the particles seems possible, no effect of PM2.5 on viral replication was observed during co-exposure, although a downregulation of IFN-ß release was associated to PM2.5 exposure. However, pre-exposure slightly increased the viral nucleoprotein production and the pro-inflammatory response. Conversely, the level of the myxovirus resistance protein A (MxA), an interferon-stimulated gene (ISG) induced by IFN-ß, was reduced. Therefore, these results suggest that pre-exposure to PM2.5 could alter the antiviral response of bronchial epithelial cells, increasing their susceptibility to viral infection.

Aerosolomics based approach to discover source molecular markers: A case study for discriminating residential wood heating vs garden green waste burning emission sources.

Biomass burning is a significant source of particulate matter (PM) in ambient air and its accurate source apportionment is a major concern for air quality. The discrimination between residential wood heating (RWH) and garden green waste burning (GWB) particulate matter (PM) is rarely achieved. The objective of this work was to evaluate the potential of non-targeted screening (NTS) analyses using HRMS (high resolution mass spectrometry) data to reveal discriminating potential molecular markers of both sources. Two residential wood combustion appliances (wood log stove and fireplace) were tested under different output conditions and wood moisture content. GWB experiments were carried out using two burning materials (fallen leaves and hedge trimming). PM samples were characterized using NTS approaches with both LC- and GC-HRMS (liquid and gas chromatography-HRMS). The analytical procedures were optimized to detect as many species as possible. Chemical fingerprints obtained were compared combining several multivariate statistical analyses (PCA, HCA and PLS-DA). Results showed a strong impact of the fuel nature and the combustion quality on the chemical fingerprints. 31 and 4 possible markers were discovered as characteristic of GWB and RWH, respectively. Complementary work was attempted to identify potential molecular formulas of the different potential marker candidates. The combination of HRMS NTS chemical characterization with multivariate statistical analyses shows promise for uncovering organic aerosol fingerprinting and discovering potential PM source markers.

Detecting and Characterizing Particulate Organic Nitrates with an Aerodyne Long-ToF Aerosol Mass Spectrometer.

Particulate organic nitrate (pON) can be a major part of secondary organic aerosol (SOA) and is commonly quantified by indirect means from aerosol mass spectrometer (AMS) data. However, pON quantification remains challenging. Here, we set out to quantify and characterize pON in the boreal forest, through direct field observations at Station for Measuring Ecosystem Atmosphere Relationships (SMEAR) II in Hyytiälä, Finland, and targeted single-precursor laboratory studies. We utilized a long time-of-flight AMS (LToF-AMS) for aerosol chemical characterization, with a particular focus to identify C x H y O z N+ ("CHON+") fragments. We estimate that during springtime at SMEAR II, pON (including both the organic and nitrate part) accounts for ∼10% of the particle mass concentration (calculated by the NO+/NO2 + method) and originates mainly from the NO3 radical oxidation of biogenic volatile organic compounds. The majority of the background nitrate aerosol measured is organic. The CHON+ fragment analysis was largely unsuccessful at SMEAR II, mainly due to low concentrations of the few detected fragments. However, our findings may be useful at other sites as we identified 80 unique CHON+ fragments from the laboratory measurements of SOA formed from NO3 radical oxidation of three pON precursors (ß-pinene, limonene, and guaiacol). Finally, we noted a significant effect on ion identification during the LToF-AMS high-resolution data processing, resulting in too many ions being fit, depending on whether tungsten ions (W+) were used in the peak width determination. Although this phenomenon may be instrument-specific, we encourage all (LTOF-) AMS users to investigate this effect on their instrument to reduce the possibility of incorrect identifications.

Modelling aerosol molecular markers in a 3D air quality model: Focus on anthropogenic organic markers.

We developed and implemented in the 3D air quality model CHIMERE the formation of several key anthropogenic aerosol markers including one primary anthropogenic marker (levoglucosan) and 4 secondary anthropogenic markers (nitrophenols, nitroguaiacols, methylnitrocatechols and phthalic acid). Modelled concentrations have been compared to measurements performed at 12 locations in France for levoglucosan in winter 2014-15, and at a sub-urban station in the Paris region over the whole year 2015 for secondary molecular markers. While a good estimation of levoglucosan concentrations by the model has been obtained for a few sites, a strong underestimation was simulated for most of the stations especially for western locations due to a probable underestimation of residential wood burning emissions. The simulated ratio between wood burning organic matter and particulate phase levoglucosan is constant only at high OM values (>10 µg m-3) indicating that using marker contribution ratio may be valid only under certain conditions. Concentrations of secondary markers were well reproduced by the model for nitrophenols and nitroguaiacols but were underestimated for methylnitrocatechols and phthalic acid highlighting missing formation pathways and/or precursor emissions. By comparing modelled to measured Gas/Particle Partitioning (GPP) of markers, the simulated partitioning of Semi-Volatile Organic Compounds (SVOCs) was evaluated. Except for nitroguaiacols and nitrophenols when ideality was assumed, the GPP for all the markers was underestimated and mainly driven by the hydrophilic partitioning. SVOCs GPP, and more generally of all SVOC contributing to the formation of SOA, could therefore be significantly underestimated by air quality models, especially when only the partitioning on the organic phase is considered. Our results show that marker modelling can give insights on some processes (such as precursor emissions or missing mechanisms) involved in SOA formation and could prove especially useful to evaluate the GPP in 3D air quality models.

Emission factors and chemical characterization of particulate emissions from garden green waste burning.

This work provides an evaluation of the emission factors (EFs) of typical garden waste burning (fallen leaves and hedge trimming) in terms of particulate matter (PM), elemental and organic carbon (EC-OC) together with a detailed chemical characterization of 88 particle-bound organic species including polycyclic aromatic hydrocarbons (PAHs), levoglucosan and its isomers, lignin breakdown products (methoxyphenols), cholesterol, alkanes, polyols and sugars. Furthermore, wood-log based burning experiments have been performed to highlight key indicators or chemical patterns of both, green waste and wood burning (residential heating) sources, that may be used for PM source apportionment purposes. Two residential log wood combustion appliances, wood stove (RWS) and fireplace, under different output conditions (nominal and reduced) and wood log moisture content (mix of beech, oak and hornbeam), have been tested. Open wood burning experiments using wood logs were also performed. Green waste burning EFs obtained were comparable to the available literature data for open-air biomass burning. For PM and for most of the organic species studied, they were about 2 to 30 times higher than those observed for wood log combustion experiments. Though, poor performance wood combustions (open-air wood log burning, fireplace and RWS in reduced output) showed comparable EFs for levoglucosan and its isomers, methoxyphenols, polyols, PAHs and sugars. Toxic PAH equivalent benzo[a]pyrene EFs were even 3-10 times higher for the fireplace and open-air wood log burning. These results highlighted the impact of the nature of the fuel burnt and the combustion performances on the emissions. Different chemical fingerprints between both biomass burning sources were highlighted with notably a predominance of odd high-molecular weight n-alkanes (higher carbon preference index, CPI), lower levoglucosan/mannosan ratio and lower sinapylaldehyde abundance for green waste burning. However, the use of such indicators seems limited, especially if applied alone, for a clear discrimination of both sources in ambient air.

Sources of particulate-matter air pollution and its oxidative potential in Europe.

Particulate matter is a component of ambient air pollution that has been linked to millions of annual premature deaths globally1-3. Assessments of the chronic and acute effects of particulate matter on human health tend to be based on mass concentration, with particle size and composition also thought to play a part4. Oxidative potential has been suggested to be one of the many possible drivers of the acute health effects of particulate matter, but the link remains uncertain5-8. Studies investigating the particulate-matter components that manifest an oxidative activity have yielded conflicting results7. In consequence, there is still much to be learned about the sources of particulate matter that may control the oxidative potential concentration7. Here we use field observations and air-quality modelling to quantify the major primary and secondary sources of particulate matter and of oxidative potential in Europe. We find that secondary inorganic components, crustal material and secondary biogenic organic aerosols control the mass concentration of particulate matter. By contrast, oxidative potential concentration is associated mostly with anthropogenic sources, in particular with fine-mode secondary organic aerosols largely from residential biomass burning and coarse-mode metals from vehicular non-exhaust emissions. Our results suggest that mitigation strategies aimed at reducing the mass concentrations of particulate matter alone may not reduce the oxidative potential concentration. If the oxidative potential can be linked to major health impacts, it may be more effective to control specific sources of particulate matter rather than overall particulate mass.

Substantial brown carbon emissions from wintertime residential wood burning over France.

Brown carbon (BrC) is known to absorb light at subvisible wavelengths but its optical properties and sources are still poorly documented, leading to large uncertainties in climate studies. Here, we show its major wintertime contribution to total aerosol absorption at 370 nm (18-42%) at 9 different French sites. Moreover, an excellent correlation with levoglucosan (r2 = 0.9 and slope = 22.2 at 370 nm), suggesting important contribution of wood burning emissions to ambient BrC aerosols in France. At all sites, BrC peaks were mainly observed during late evening, linking to local intense residential wood burning during this time period. Furthermore, the geographic origin analysis also highlighted the high potential contribution of local and/or small-regional emissions to BrC. Focusing on the Paris region, twice higher BrC mass absorption efficiency value was obtained for less oxidized biomass burning organic aerosols (BBOA) compared to more oxidized BBOA (e.g., about 4.9 ± 0.2 vs. 2.0 ± 0.1 m2 g-1, respectively, at 370 nm). Finally, the BBOA direct radiative effect was found to be 40% higher when these two BBOA fractions are treated as light-absorbing species, compared to the non-absorbing BBOA scenario.

Analysis and determination of secondary organic aerosol (SOA) tracers (markers) in particulate matter standard reference material (SRM 1649b, urban dust).

Secondary organic aerosol (SOA) accounts for a significant fraction of particulate matter (PM) in the atmosphere. Source identification, including the SOA fraction, is critical for the effective management of air pollution. Molecular SOA markers (tracers) are key compounds allowing the source apportionment of SOA using different methodologies. Therefore, accurate SOA marker measurements in ambient air PM are important. This study determined the concentrations of 12 key SOA markers (biogenic and anthropogenic) in the urban dust standard reference material available from the National Institute of Standards and Technology (NIST) (SRM 1649b). Two extraction procedures, sonication and QuEChERS-like (quick easy cheap effective rugged and safe), have been compared. Three research laboratories/institutes using two analytical techniques (gas chromatography/mass spectrometry (GC/MS) and ultra-high-pressure liquid chromatography/tandem mass spectrometry (HPLC/MS-MS)) carried out the analyses. The results obtained were all in good agreement, except for 2-methylerythritol. The analysis of this compound still seems to be challenging by both GC/MS (large injection repeatability) and HPLC/MS-MS (separation issues of both 2-methyltetrols: 2-methylthreitol and 2-methylerythritol). Possible inhomogeneity in the SRM for this compound could also explain the large discrepancies observed. Sonication and QuEChERS-like procedures gave comparable results for the extraction of the SOA markers showing that QuEChERS-like extraction is suitable for the analysis of SOA markers in ambient air PM. As this study provides, for the first time, indicative values in a reference material for typical SOA markers, the analysis of SRM 1649b (urban dust) could be used for quality control/assurance purposes. Graphical abstract.

Speciation of organic fraction does matter for source apportionment. Part 1: A one-year campaign in Grenoble (France).

PM10 source apportionment was performed by positive matrix factorization (PMF) using specific primary and secondary organic molecular markers on samples collected over a one year period (2013) at an urban station in Grenoble (France). The results provided a 9-factor optimum solution, including sources rarely apportioned in the literature, such as two types of primary biogenic organic aerosols (fungal spores and plant debris), as well as specific biogenic and anthropogenic secondary organic aerosols (SOA). These sources were identified thanks to the use of key organic markers, namely, polyols, odd number higher alkanes, and several SOA markers related to the oxidation of isoprene, α-pinene, toluene and polycyclic aromatic hydrocarbons (PAHs). Primary and secondary biogenic contributions together accounted for at least 68% of the total organic carbon (OC) in the summer, while anthropogenic primary and secondary sources represented at least 71% of OC during wintertime. A very significant contribution of anthropogenic SOA was estimated in the winter during an intense PM pollution event (PM10>50µgm-3 for several days; 18% of PM10 and 42% of OC). Specific meteorological conditions with a stagnation of pollutants over 10days and possibly Fenton-like chemistry and self-amplification cycle of SOA formation could explain such high anthropogenic SOA concentrations during this period. Finally, PMF outputs were also used to investigate the origins of humic-like substances (HuLiS), which represented 16% of OC on an annual average basis. The results indicated that HuLiS were mainly associated with biomass burning (22%), secondary inorganic (22%), mineral dust (15%) and biogenic SOA (14%) factors. This study is probably the first to state that HuLiS are significantly associated with mineral dust.

Evaluation of a Conceptual Model for Gas-Particle Partitioning of Polycyclic Aromatic Hydrocarbons Using Polyparameter Linear Free Energy Relationships.

A model for gas-particle partitioning of polycyclic aromatic hydrocarbons (PAHs) was evaluated using polyparameter linear free energy relationships (ppLFERs) following a multiphase aerosol scenario. The model differentiates between various organic (i.e., liquid water-soluble (WS)/organic soluble (OS) organic matter (OM), and solid/semisolid organic polymers) and inorganic phases of the particulate matter (PM). Dimethyl sulfoxide and polyurethane were assigned as surrogates to simulate absorption into the above-mentioned organic phases, respectively, whereas soot, ammonium sulfate, and ammonium chloride simulated adsorption processes onto PM. The model was tested for gas and PM samples collected from urban and nonurban sites in Europe and the Mediterranean, and the output was compared with those calculated using single-parameter linear free energy relationship (spLFER) models, namely Junge-Pankow, Finizio, and Dachs-Eisenreich. The ppLFER model on average predicted 96 ± 3% of the observed partitioning constants for semivolatile PAHs, fluoranthene, and pyrene, within 1 order of magnitude accuracy with root-mean-square errors (RMSE) of 0.35-0.59 across the sites. This was a substantial improvement compared to Finizio and Dachs-Eisenreich models (37 ± 17 and 46 ± 18% and RMSE of 1.03-1.40 and 0.94-1.36, respectively). The Junge-Pankow model performed better among spLFERs but at the same time showed an overall tendency for overestimating the partitioning constants. The ppLFER model demonstrated the best overall performance without indicating a substantial intersite variability. The ppLFER analysis with the parametrization applied in this study suggests that the absorption into WSOSOM could dominate the overall partitioning process, while adsorption onto salts could be neglected.

On-road traffic emissions of polycyclic aromatic hydrocarbons and their oxy- and nitro- derivative compounds measured in road tunnel environments.

Vehicular emissions are a key source of polycyclic aromatic compounds (PACs), including polycyclic aromatic hydrocarbons (PAHs) and their oxygenated (OPAH) and nitrated (NPAH) derivatives, in the urban environment. Road tunnels are a useful environment for the characterisation of on-road vehicular emissions, providing a realistic traffic fleet and a lack of direct sunlight, chemical reactivity and non-traffic sources. In the present investigation the concentrations of selected PAHs, OPAHs and NPAHs have been measured in the Parc des Princes Tunnel in Paris (PdPT, France), and at the Queensway Road Tunnel and an urban background site in Birmingham (QT, U.K). A higher proportion of semi-volatile (3-4 ring) PAH, OPAH and NPAH compounds are associated with the particulate phase compared with samples from the ambient environment. A large (~85%) decline in total PAH concentrations is observed between 1992 and 2012 measurements in QT. This is attributed primarily to the introduction of catalytic converters in the U.K as well as increasingly stringent EU vehicle emissions legislation. In contrast, NPAH concentrations measured in 2012 are similar to those measured in 1996. This observation, in addition to an increased proportion of (Phe+Flt+Pyr) in the observed PAH burden in the tunnel, is attributed to the increased number of diesel passenger vehicles in the U.K during this period. Except for OPAHs, comparable PAH and NPAH concentrations are observed in both investigated tunnels (QT and PdP). Significant differences are shown for specific substances between PAC chemical profiles in relation with the national traffic fleet differences (33% diesel passenger cars in U.K. vs 69% in France and up to 80% taking into account all vehicle categories). The dominating and sole contribution of 1-Nitropyrene observed in the PdPT NPAH profile strengthens the promising use of this compound as a diesel exhaust marker for PM source apportionment studies.

One-year study of polycyclic aromatic compounds at an urban site in Grenoble (France): Seasonal variations, gas/particle partitioning and cancer risk estimation.

21 PAHs, 27 oxy-PAHs and 32 nitro-PAHs were measured every third day over a year in both gaseous (G) and particulate PM10 (P) phases in ambient air of Grenoble (France). Mean total concentrations (G+P) of PAHs and oxy-PAHs were in the same range and about 10ngm(-3). Nitro-PAHs were 50 to 100 times less concentrated averaging 100pgm(-3). Polycyclic aromatic compound (PAC) concentrations were 5 to 7 times higher in "cold" period (October to March) than in "warm" period (April to September). Seasonal variations may be explained by higher primary emissions from residential heating, especially biomass burning in "cold" season. Meteorological conditions and influence of the geomorphology around Grenoble, with the formation of thermal inversion layers leading to the stagnation of pollutants, were additional key parameters. Maximum individual PAC concentrations were observed during two PM10 pollution events in December and February-March. Chemical processes and secondary formation of oxy- and nitro-PAH were probably enhanced by the accumulation of the pollutants during these events. PAC gas/particle partitioning depended on compound molecular weight and vapour pressure. Gas/particle partitioning of oxy- and nitro-PAHs were evaluated using a multi-phase poly-parameter linear free energy relationship model. The PAC cancer risk was assessed using toxic equivalency factors available in the literature (19 PAHs, 10 nitro-PAHs and 1 oxy-PAH). Overall, particle-bound PACs contributed about 76% of the cancer risk. While PAHs accounted for most of the total PAC cancer risk, oxy- and nitro-PAHs could account for up to 24%. The risk quantification across substance classes is limited by toxicological data availability.

Atmospheric reactions of 9,10-anthraquinone.

The probably carcinogenic compound 9,10-anthraquinone is mainly existing in the atmosphere in the particulate phase and is often detected and measured among other oxygenated PAHs in atmospheric samples. Its fate, once released or formed in the atmosphere, still remains unknown. In this work, heterogeneous chemical oxidation processes of 9,10-anthraquinone were investigated with ozone (O3), nitrogen dioxide (NO2) and hydroxyl radical (OH). The study of 9,10-anthraquinone adsorbed on silica particles showed no reactivity with O3 and NO2. On the other hand, the reaction with OH radicals was observed and led to the formation of 1-hydroxy-9,10-anthraquinone, another oxidation product recognized as possibly carcinogenic to humans. This study showed that reactions with ozone and nitrogen dioxide are unlikely to contribute to atmospheric degradation of 9,10-anthraquinone, whereas reactions with OH radicals could be involved in 9,10-anthraquinone degradation processes, even if such reaction is probably very slow under ambient conditions.

Diurnal/nocturnal concentrations and sources of particulate-bound PAHs, OPAHs and NPAHs at traffic and suburban sites in the region of Paris (France).

Particulate concentrations of polycyclic aromatic compounds (PACs) including, 17 polycyclic aromatic hydrocarbons (PAHs), 9 oxygenated PAHs (OPAHs) and 18 nitrated PAHs (NPAHs) were determined at traffic and suburban sites located in the region of Paris. A 12 h sampling basis time resolution was applied in order to study their diurnal and nocturnal variations. Observed concentrations were about 10 times higher at the traffic site for all compounds and were higher during the night-time for both sites (except for NPAHs at the traffic site). No significant differences in PAH and OPAH profiles were observed at both sites whereas, for NPAHs, 1-nitropyrene (diesel source) was the most abundant at the traffic site and 2+3-nitrofluoranthene (secondary formed by gas-phase reaction) was predominant at the suburban site. The study of the specific ratio 2-nitrofluoranthene/1-nitropyrene (2-NFlt/1-NP) showed a local formation of NPAHs in gaseous phase at the suburban site. A detailed analysis showed that atmospheric humidity and rainfalls modified differently PAH and NPAH profiles, in comparison to OPAH. A difference of the scale variability of water solubility between, light (MW≤228 g mol(-1)) and heavy compounds (MW≥273 g mol(-1)), could explain these observations. The specific study of the relationships between PACs and other measured pollutants highlighted that particle resuspension could constitute a significant source of PM on the traffic site. Even if NPAH formation seemed clearly evident at the suburban site during periods characterised by high O(3) and NO(2) concentration levels, results showed also that the primary and/or secondary origins of OPAHs and NPAHs were strongly dependent on the sampling site and on sampling conditions. Finally, we conclude that higher time sampling resolutions would be helpful in investigating the atmospheric chemistry and behaviours of PACs in correlation with the local meteorological variations and the daily cycle of human activities.

Phototransformation processes of 2,4-dinitrophenol, relevant to atmospheric water droplets.

This paper shows that the polychromatic quantum yield for the photolysis of 2,4-dinitrophenol (24DNP) in the wavelength interval of 300-500 nm is (8.1+/-0.4) x 10(-5) for the undissociated phenol, and (3.4+/-0.2) x 10(-5) for the phenolate. The second-order rate constants for reaction with ()OH were determined here as (1.76+/-0.05) x 10(9) M(-1) s(-1) and (2.33+/-0.11) x 10(9) M(-1) s(-1) for the phenol and the phenolate, respectively. By combining laboratory results and a simple modelling approach of the atmospheric aqueous phase, this work shows that the direct photolysis and the reaction with ()OH would play a comparable role in the degradation of 24DNP at pH>4. The ()OH reaction would prevail for pH<4. Both pathways would be more important than the night-time reaction with *NO(3) as removal processes for 24DNP in the atmospheric waters.

UVA irradiation induces direct phototransformation of 2,4-dinitrophenol in surface water samples.

Lake water samples spiked with 2,4-dinitrophenol (24DNP) were irradiated under artificial UVA irradiance. It was found that the direct photolysis is the main photodegradation pathway of 24DNP in lake water. On the lake water samples it was also determined the formation and consumption rates of *OH, by means of the transformation reaction of benzene into phenol. It was found that the rate of direct photolysis prevails over the *OH phototransformation rate by one-two orders of magnitude. Moreover, the excited triplet states of chromophoric dissolved organic matter and singlet oxygen are expected to play a negligible role in the photodegradation of 24DNP. By modelling the direct photolysis of 24DNP in surface water bodies, one gets a half-life time of 2-10 summer sunny days for water-column depths up to 10 m. This would make the direct photolysis a major pathway for the transformation of 24DNP in freshwaters.

Photochemical generation of reactive species upon irradiation of rainwater: negligible photoactivity of dissolved organic matter.

This paper focuses on the study of the photochemical activity of dissolved organic matter present in rainwater. Formation rates of the reactive species hydroxyl radical (OH(*)), singlet oxygen ((1)O(2)) and dissolved organic matter triplet states ((3)DOM()) were determined by irradiation (UV-A) of wet-only rainwater samples collected in Turin (Italy) in the presence of specific scavengers (benzene, furfuryl alcohol and phenol, respectively). Photo-formation rates of OH(*) ( approximately 3.10(-)(11)Ms(-)(1)) and (1)O(2) ( approximately 10(-)(14)Ms(-)(1)) were lower (1 or 2 orders of magnitude) or largely lower (4 to 10 orders of magnitude) than those determined for fog and cloud samples in previous studies. (3)DOM() formation rate values were either negligible or quite low ( approximately 10(-)(12)Ms(-)(1)) by comparison with those evaluated for surface water samples. Deduced steady-state [OH(*)] were in the same range as those reported for fog samples in the literature (8.7.10(-)(16) to 1.5.10(-)(15)M), while [(1)O(2)] was often several orders of magnitude lower and, therefore, could be considered as negligible. Nitrite (NO(2)(-)) constituted the main source of OH(*) (69 + or - 21 to 138 + or - 36%), and the deduced contribution of DOM was low or nil. All the results obtained in this study tend to demonstrate that DOM (including HUmic LIke Substances, HULIS) present in rainwater is poorly or not photoactive. Therefore, there could be considerable difference between rainwater DOM (HULIS included) and the organic matter present in surface waters, particularly the humic substances, as far as the photochemical activity is concerned.

A new ozone denuder for aerosol sampling based on an ionic liquid coating.

A new ionic liquid 1-octyl-3,5-dimethylpyridinium iodide ([O35LUT](+)[I](-)) was synthesized and utilized as coating for an ozone denuder device based on a high-volume aerosol sampler (30 m(3) h(-1)). Particle transmission of the denuder was studied, and over 99% of particles ranging from 10 to 2,500 nm were transmitted. The device, containing 4.66 g of ionic liquid, was used outdoors, under dry and damp atmospheric conditions. In order to expose the device to an average concentration of 120 ppbv (240 microg m(-3)) of ozone in air, an additional production of ozone was directly injected into the denuder. Under these conditions, over 97% of ozone was removed for approximately 120 h (5 days). Therefore, iodide-based ionic liquids can be used as a new alternative to conventional denuder coatings in order to reduce artifacts occurring during sampling of particulate matter. Future applications are not limited to ozone removal for specific aerosol sampling methods.

Polycyclic aromatic hydrocarbons (PAHs), nitrated PAHs and oxygenated PAHs in ambient air of the Marseilles area (South of France): concentrations and sources.

Ambient measurements (gas+particle phases) of 15 polycyclic aromatic hydrocarbons (PAHs), 17 nitrated PAHs (NPAHs) and 9 oxygenated PAHs (OPAHs) were carried out during July 2004 on three different sites (urban, sub-urban and rural) in the region of Marseilles (South of France). Atmospheric concentrations of these classes of polyaromatics are great of interest because of their high potential mutagenicity and carcinogenicity. OPAH concentrations were of the same order of magnitude as those of PAHs while NPAH concentrations were one to two orders lower. 9-Fluorenone and 9,10-anthraquinone were the most abundant OPAHs, accounting for about 60% and 20% of the total OPAH concentration. Respectively 1-and 2-nitronaphthalene were the most abundant NPAHs and were accounting for about 30-50% and 15-30% of the total NPAH concentration. NPAHs and OPAHs concentration levels were consistent with the characteristics of the sampling sites. Study of source specific ratios (2-nitrofluoranthene/1-nitropyrene) clearly showed those primary NPAH sources influence the urban and sub-urban sites whereas production of secondary NPAHs by gas phase reactions was prevalent at the rural site. The study of NPAH and OPAH sources suggested that gasoline engines were an important source of such compounds Whereas the dominant source of 1-nitropyrene, 2-nitrofluorene, 6-nitrochrysene and benz[a]anthracene-7,12-dione seems to be diesel vehicles. Finally, 9,10-anthraquinone presents a double origin: primary diesel emission and photochemical processes. Formation of 9,10-anthraquinone from anthracene ozonation was shown at the rural site. Further investigations will be necessary in order to discriminate when (before or during the sampling) the OPAHs are formed.