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Studies have shown that biogenic compounds, long chain secondary compounds and long lifetime anthropogenic compounds are involved in the formation of organic aerosols in both polluted areas and remote places. This work aims at developing an active sampling method to monitor these compounds (i.e. 6 straight-chain saturated aldehydes from C6 to C11; 8 straight-chain alkanes from C9 to C16; 6 monoterpenes: α-pinene, β-pinene, camphene, limonene, α-terpinene, & γ-terpinene; and 5 aromatic compounds: toluene, ethylbenzene, meta-, para- and ortho-xylenes) in remote areas. Samples are collected onto multi-bed sorbent cartridges at 200 mL min(-1) flow rate, using the automatic sampler SyPAC (TERA-Environnement, Crolles, France). No breakthrough was observed for sampling volumes up to 120 L (standard mixture at ambient temperature, with a relative humidity of 75%). As ozone has been shown to alter the samples (losses of 90% of aldehydes and up to 95% of terpenes were observed), the addition of a conditioned manganese dioxide (MnO(2)) scrubber to the system has been validated (full recovery of the affected compounds for a standard mixture at 50% relative humidity--RH). Samples are first thermodesorbed and then analysed by GC/FID/MS. This method allows suitable detection limits (from 2 ppt for camphene to 13 ppt for octanal--36 L sampled), and reproducibility (from 1% for toluene to 22% for heptanal). It has been successfully used to determine the diurnal variation of the target compounds (six 3 h samples a day) during winter and summer measurement campaigns at a remote site in the south of France.

An ultra-performance liquid chromatographic-atmospheric pressure chemical ionization time-of-flight mass spectrometric (UPLC-APCIToFMS) method for rapid analysis of twelve nitrated polycyclic aromatic hydrocarbons (NPAHs) and nine oxygenated polycyclic aromatic hydrocarbons (OPAHs) in particle samples has been developed. The extraction step using pressurized liquid extraction was optimized by experimental design methods and the concentrated extracts were analyzed without further clean-up. Matrix effects resulting in suppression or enhancement of the response during the ionization step were not observed. The suitability of the developed method is demonstrated by analysis of six different particle samples including standard reference materials, atmospheric particles collected by a high-volume sampler at an urban background site, and a soot sample from a burner. Results from these measurements showed clear differences between the different kinds of samples. Concentrations from reference materials are in good agreement with those from previous studies. Additionally a clear seasonal trend could be observed in atmospheric NPAH and OPAH concentrations found in real samples, with higher concentrations in winter.

An ultra-high-performance liquid chromatography/time-of-flight mass spectrometry (with negative ion electrospray ionization) methodology was developed for the simultaneous quantification of benzoic acid and 15 long-chain monocarboxylic acids (MCAs) in ambient aerosols. A fast and quantitative pressurized fluid extraction procedure was optimized using experimental design and the extracts were analyzed without any further clean-up step. Chromatographic separation was achieved on a BEH-C18 column with a mobile phase consisting of 5 mM formic acid in water/acetonitrile (90:10, v/v) and methanol. Excellent precision and accuracies in the MS mass measurements were observed. The method was validated using actual samples spiked with a solution containing either standards or 13C-surrogates. Matrix effects were observed for the C14 MCA only. It was then applied to air particulate reference materials and atmospheric samples collected by a low-volume sampler.

There is a considerable interest in quantifying near-surface ozone concentrations and associated trends, as they serve to define the impacts on ozone of the anthropogenic precursors reductions and to evaluate the effects of emission control strategies. A statistical test has been used to the ozone air concentrations measured in the French rural monitoring network stations, called MERA, in order to bring out spatio-temporal trends in air quality in France over the 1995-2003 period. The non-parametric Mann-Kendall test has been developed for detecting and estimating monotonic trends in the time series and applied in our study at annual values: mean, 98th percentile and median based on hourly averaged ozone concentrations and applied to daily maxima. In France, when averaged overall 9 stations between 1995 and 2003, a slight increasing trend of the O(3) levels (+0.6 +/- 1.3% year( - 1)) is observed, which is strongly influenced by the concentrations of the high altitude stations. In stations below 1000 m a mean rate of -0.48% year( - 1) from annual average concentrations, of -0.45% year( - 1) for medians and of +0.56% year( - 1) for P.98 over the 1995-2003 period were obtained. In stations above 1,000 m a mean rate of +1.75% year( - 1) from annual averages values, of +4.05% year( - 1) for medians and of +2.55% year( - 1) for P.98 were calculated over the 1997-2003 period. This situation is comparable to the one observed in other countries. In Europe and in France a reduction of precursor emissions is observed whereas a slight increasing trend of the O(3) levels is observed over the 1995-2003 period. One reason is the non-linearity of chemical ozone production with respect to precursor emissions. Possible explanations are an increase in near-surface ozone values caused by a reduced ozone titration by reduced NO( x ), the meteorological parameters change, an increase in bio-geogenic compound concentrations, the intercontinental transport from North America and Asia and the influence of stratospheric-tropospheric exchanges. These possible explanations must be interpreted carefully as on the short time scales considered.

Determination of trace contents of metals and metalloids, monitored in airborne particles for their adverse health and environmental impact or to discriminate pollutant particulate emission sources, requires very sensitive analytical methods. Dynamic reaction cell inductively coupled plasma mass spectrometry (DRC-ICP-MS) has been applied to measure ultra-trace elements found in PM10 atmospheric particles in order to determine simultaneously, rapid and accurate concentrations for well known highly interfered isotopes (75As, 59Co, 52Cr, 53Cr, 58Ni, 60Ni, 78Se, 45Sc, and 51V). The challenge resides in the extremely low content of these elements encountered in PM10 particles, while thorough mineralization procedures in complex matrices are necessary to deal with refractory minerals. The potentially interfering polyatomic ions combining Ar, Cl, F, O, N, and C isotopes were significantly reduced by using NH3 as the reaction gas in the DRC, optimizing the reaction cell band pass and tuning of the gas flow rate. Standard Reference Material (NIST 1648) as well as real atmospheric samples were analyzed under the best defined conditions to validate and exemplify our methodology. The method detection limits are 450 ng/L for As, 13 ng/L for Co, 1210 ng/L for Cr, 780 ng/L for Ni, 47 ng/L for Se, 22 ng/L for Sc, and 26 ng/L for V. Based on real atmospheric sample measurements, DRC-ICP-MS associated with NH3 is confirmed as a cost effective technique to produce accurate results during routine working procedures for all these elements except Se.

This study examined the performances of a thermal desorbable radial diffusive sampler for the weekly measurement of eight glycol ethers in indoor air and described the results of an application of this method carried out as part of HABIT'AIR Nord - Pas de Calais program for the air monitoring of these compounds in sixty homes located in northern France. The target compounds were the four glycol ethers banned from sale to the public in France since the 1990s (i.e. 2-methoxy ethanol, 2-ethoxy ethanol and their acetates) and four other glycol ethers derivatives of which the use have increased considerably (i.e. 1-methoxy-2-propanol, 2-butoxy ethanol and their acetates).A test program was carried out with the aim of validating the passive sampling method. It allowed the estimation of all the parameters of a method for each compound (calibration, analytical precision, desorption efficiency, sampling rate in standard conditions, detection limit and stability of sample before and after exposure), the examination of the influence of environmental factors on the sampling rate by some exposure chamber experiments and the assessment of the uncertainty of the measurements. The results of this evaluation demonstrated that the method has turned out to be suitable for six out of eight glycol ethers tested. The effect of the environmental factors on the sampling rates was the main source of measurement uncertainty. The measurements done in sixty homes revealed a relative abundance of 1-methoxy-2-propanol that was found in more than two thirds of homes at concentration levels of 4.5 microg m(-3) on average (a maximum value of 28 microg m(-3)). 1-methoxy-2-propanol acetate and 2-butoxy ethanol were also detected, but less frequently (in 19% of homes) and with the concentrations below 12 microg m(-3). The highest levels of these glycol ethers appear to be in relation to the emissions occurring at the time of cleaning tasks.

The global objective of this two part study was (1) to conduct VOC measurements in order to further understand VOC behaviour in an urban area influenced by industrial emissions and (2) to evaluate the role of these specific sources relative to urban sources. In this first paper a thorough descriptive and qualitative analysis is performed. A second article will be devoted to the quantitative analysis using Chemical Mass Balance (CMB) modelling. In the Dunkerque (France) area most industrial sources are situated in the north and the west of the receptor site whereas urban and traffic sources are located in the south and the east. A data set constituted of nearly 330,000 VOC data has been developed from the hourly measurements of 53 VOCs for 1 year from September 2002 to August 2003. It also contains meteorological parameters such as temperature, wind direction and wind speed. Using different graphical methods, the influence of the different sources on the ambient VOC concentrations has been highlighted at different time scales. In this work, the analysis of daily time series for the 53 VOCs shows the influence of traffic exhaust emissions because of the increases at traffic rush hours. Besides, the seasonal evolution of the VOC/acetylene ratio points out the influence of evaporative sources on ambient VOC concentration. Concerning other point sources, the variations of measured VOC concentrations for different wind directions and scatter plots of VOC hourly concentrations highlight the influence of some industrial sources.

In Part I of this study (Badol C, Locoge N, Leonardis T, Gallo JC. Using a source-receptor approach to characterise VOC behaviour in a French urban area influenced by industrial emissions, Part I: Study area description, data set acquisition and qualitative data analysis of the data set. Sci Total Environ 2007; submitted as companion manuscript.) the study area, acquisition of the one-year data set and qualitative analysis of the data set have been described. In Part II a source profile has been established for each activity present in the study area: 6 profiles (urban heating, solvent use, natural gas leakage, biogenic emissions, gasoline evaporation and vehicle exhaust) have been extracted from literature to characterise urban sources, 7 industrial profiles have been established via canister sampling around industrial plants (hydrocarbon cracking, oil refinery, hydrocarbon storage, lubricant storage, lubricant refinery, surface treatment and metallurgy). The CMB model is briefly described and its implementation is discussed through the selection of source profiles and fitting species. Main results of CMB modellings for the Dunkerque area are presented. (1) The daily evolution of source contributions for the urban wind sector shows that the vehicle exhaust source contribution varies between 40 and 55% and its relative increase at traffic rush hours is hardly perceptible. (2) The relative contribution of vehicle exhaust varies from 55% in winter down to 30% in summer. This decrease is due to the increase of the relative contribution of hydrocarbon storage source reaching up to 20% in summer. (3) The evolution of source contributions with wind directions has confirmed that in urban wind sectors the contribution of vehicle exhaust dominate with around 45-55%. For the other wind sectors that include some industrial plants, the contribution of industrial sources is around 60% and could reach 80% for the sector 280-310 degrees , which corresponds to the most dense industrial area. (4) The pollution in Dunkerque has been globally characterised taking into account the frequency of wind directions and contributions of sources in each wind direction for the whole year. It has been concluded that contribution of industrial sources is below 20% whereas vehicle exhaust contribution is superior to 40%.

Simulation chamber experiments have been carried out at room temperature to investigate the products of the acetone + OH and acetone-d6 + OH reactions using two photoreactors made of Teflon or Pyrex and coupled to GC-FTIR-FID analytical techniques. In the Pyrex chamber, the results demonstrated that the channel forming acetic acid is a minor oxidation route in the atmospheric acetone-h6 + OH reaction (yield <5%), whereas a higher yield of about 20% was obtained in the case of the acetone-d6 + OH reaction, in good agreement with previous studies. Existence of a heterogeneous way of formation of acetic acid has also been identified in the Teflon photoreactor.

Personal NO(2) exposure measurements were achieved during two campaigns in a large northern France city. These campaigns were following an innovating approach based on sequential exposure measurements by diffusive samplers distinguishing four categories of microenvironments ("home", "other indoor places", "transport" and "outdoors"). The objective of these campaigns was to obtain NO(2) personal exposure data in different microenvironments and to examine the determinants of personal exposure to this pollutant. Each campaign comprised two 24-h sampling periods: one during a working day and the second during the weekend. The average total NO(2) personal exposure ranged from 17 microg m(-3) for the summer weekend samplings to 38 microg m(-3) for the winter weekday samplings. The highest levels were found in transports and outdoors, the intermediate ones in other indoor places and the lowest in homes. Despite their weak levels, indoor environments contributed for more than 78% to total NO(2) personal exposure because of more time spent in these living places. A Multiple Correspondence Analysis (MCA) highlighted the determinants of NO(2) personal exposure in the "home" and "transport" microenvironments. This led to a classification of NO(2) personal exposure levels according to different means of transport: from the lowest to the highest exposure levels, train, tramway or underground, bicycle, car or motorcycle. In homes, the rise of NO(2) personal exposures is mainly due to the use of gas stoves and gas heating and the absence of automatic airing system. A classification of NO(2) personal exposure levels was set up according to the characteristics of homes. An analysis of correlations between the home NO(2) personal exposures and outdoor concentrations measured by fixed ambient air monitoring stations showed weak relations suggesting that the data of these stations are poor predictors of NO(2) personal exposures in homes.

Radiello((R)) diffusive samplers filled with a thermally desorbable adsorbent (graphitised charcoal Carbograph 4) have been tested for the monitoring of BTEX. The sampling rates have been estimated under various controlled atmospheres in order to evaluate the effects of two factors (exposure time, concentration levels and their interaction) on the performances of the Radiello((R)) sampler. Experiments have been carried out under various atmospheres in exposure chamber. A total of 174 Radiello((R)) samplers were exposed while varying two conditions: exposure time (1, 3, 7 and 14 days) and BTEX concentrations (low, medium and high levels). The results show that the sampling rates of benzene and toluene decrease for exposure of 14 days and especially for high concentration levels: decrease of 30% at 10mugm(-3) for benzene and 14% at 30mugm(-3) for toluene. To try to explain the variations of these sampling rates, the breakthrough volumes (V(B)) of BTEX on Carbograph 4 have been determined at different temperature and concentration conditions in order to evaluate the Langmuir parameters and their adsorption enthalpy (-DeltaH(ads)) using the Van't Hoff equation. With regard to these adsorption characteristics, the dependence of sampling rates with concentration level and exposure time were analysed and discussed.

Fifty non-methane hydrocarbons (NMHC) and seventeen carbonyl compounds were measured at a French rural site from 1997 to 2001, as part of the EMEP programme. Data handling was based on an original source-receptor approach. First, the examination of the levels and trends was completed by the comparison of the seasonal distribution of rural and urban VOC/acetylene ambient ratios. This analysis has shown that most of the compounds derived from mixing and photochemical transformation of mid-range transported urban pollutants from the downwind urban area. Then, identified sources and sinks were temporally apportioned. Urban air masses mixing explains, at least, 80% of the wintertime levels of anthropogenic NMHC and isoprene. In summer, photochemistry dominates the day-to-day distribution of anthropogenic NMHC whilst summertime isoprene is also controlled by in-situ biogenic emissions. Then, the results of C(1)-C(3) carbonyls were discussed with respect to their direct biogenic and anthropogenic emissions and photochemical production through the [carbonyl/auto-exhaust tracers] emission ratio. Diluted vehicle exhaust emissions mainly contribute to the total content of lower aldehydes in winter while other processes control lower ketones. Secondary production is predominant in summer with at least a 50% high intensity. Its dependence upon temperature and radiation is also demonstrated. Finally, the importance of the primary and secondary biogenic production of acetone and formaldehyde is assessed. In particular, biogenic contribution would explain 37 +/- 25% of acetone levels in summer.

An automated system for the monitoring of volatile organic compound (VOC) ozone precursors in ambient air is described. The measuring technique consists of subambient preconcentration on a cooled trap followed by thermal desorption and GC/FID analysis. First, the technical development, which permits detection limits below 0.05 ppbv to be reached, proceeded in two steps: (1). the determination of optimum sampling parameters (trap composition and conditioning, outlet split, desorption temperature); (2). the development of a reliable calibration method based on a highly accurate standard. Then, a 4-year field application of the hourly measuring chain was carried out at two urban sites. On the one hand, quality control procedures provided the best VOC identification (peak assignment) and quantification (reproducibility, blank system control). On the other hand, the success and performances of the routine experience (88% of the measurements covered more than 40 target compounds) indicated the high quality and suitability of the instrumentation which is actually applied in several French air quality monitoring networks. Finally, an example of data analysis is presented. Data handling identified important organic compound sources other than vehicle exhaust.

This study explains the main characteristics of a new passive sampler which is able to give reliable nitrogen dioxide measurements for short time sampling. The sampling rate was found to be on average 0.89 cm3 s(-1) for indoor sampling and 1.00 cm3 s(-1) for outdoor sampling. The detection limit was evaluated at 11 microg m(-3) for a one-hour measurement. In field conditions, the passive sampler measurements were in agreement with those of the chemiluminescent NOx monitors. Measurement uncertainties were estimated at 34% and 38% for laboratory tests in conditions corresponding respectively to indoor and outdoor measurements and were evaluated at 28 to 37% depending on the nitrogen dioxide concentration for field experiments. The effects of various factors on the passive sampler were determined in an exposure chamber. The sampling rate of the retained sampler version was not significantly influenced by wind speeds superior to 0.3 m s(-1). A decrease of the uptake rate is observed for high nitrogen dioxide doses. The sampling rate increases linearly with temperature (2% per degree C). The relative humidity has only a weak effect.

The performances and applicability of a diffusion tube sampler for the simultaneous measurements of NO2 and SO2 in ambient air were evaluated. SO2 and NO2 are collected by the passive sampler using triethanolamine as trapping agent and are determined as sulphate and nitrite with ion chromatography. The detection limit (2.3 microg m(-3) of NO2 and 4.2 microg m(-3) of SO2 for two weeks sampling) is adequate for the determination of concentrations in urban and industrial areas. Precision of the method as RSD is in mean 5% for NO2 and 12% for SO2 at the concentration levels in urban areas. Calibration of the method was performed in the field conditions by comparison between the responses of sampler and the concentrations measured by the continuous monitors. High degree of linearity (correlation coefficients > 0.8) is found between the passive sampler tube and the continuous monitor data for both NO2 and SO2. To reduce the wind velocity influence on passive sampling of diffusion tubes, a protective shelter was tested in this study. The overall uncertainty of one measure for the optimised method is estimated at 5 microg m(-3) for NO2 and 6 microg m(-3) for SO2. Suitability of this passive sampling method for air pollution monitoring in urban areas was demonstrated by the results shown in this paper on a campaign carried out in the French agglomeration.

Continuous hourly air quality data involving 37 C2-C9 non-methane hydrocarbons (NMHC) over 4 years are reported for the first time in Lille metropol, northern France, at two urban roadside and background sites. The data have been analysed in two complementary steps: univariate statistics which define the spatial and temporal characteristics of NMHC by constructing the seasonal and daily concentration profiles, and multivariate statistics based on principal component analysis (PCA). A number of important sources have been clearly identified depending on the season: (1) motor vehicle exhaust, which dominates the NMHC distribution and particularly in winter, even for isoprene; (2) wintertime stationary combustion and activities related to fossil fuel consumption in general, such as natural gas leakage of ethane and propane; (3) summertime evaporative emissions from fuel and solvent; and (4) summertime biogenic emissions through isoprene behaviour and their dependence on temperature.

A method was developed for the elemental analysis of size segregated particles ranging from 0.03 to 10 microns. Sampling and analysis problems are discussed in this paper. Particles were collected with a Dekati low-pressure cascade impactor. PTFE filters coated with oleic acid were used as substrate. Particles were microwave digested in closed vessels. The optimum digestion mixture was composed of HNO3 (1 mL), HF (50 microL) and H2O (1 mL). The optimal power setting and digestion time were studied in order to achieve an efficient digestion. A ca. 35 min microwave digestion cycle at a 650 W maximum power allowed complete digestion of the samples. Special emphasis was placed on the pressure in the closed vessels to avoid sample losses. Solution samples were analysed by inductively coupled plasma optical emission spectrometry using an ultrasonic nebuliser for 18 elements (Al, Ba, Ca, Cd, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, S, Sr, Ti, V, Zn). This procedure was tested with NIST Standard Reference Material 1648 Urban Particulate. Recoveries for certified elements ranged from 95 to 105% except for Al (90%). The influence of cascade impactor materials was investigated with 44 field samples. Strong artefacts due to contamination were shown for analysis at environmental concentrations of Al, Cr, Mn and Ni.