Passive sampling of glycol ethers and their acetates in indoor air

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.     

Development of a sampling method for the simultaneous monitoring of straight-chain alkanes, straight-chain saturated carbonyl compounds and monoterpenes in remote areas

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.     

Determination of 14 amines in air samples using midget impingers sampling followed by analysis with ion chromatography in tandem with mass spectrometry

An Ion Chromatography-Mass Spectrometry (IC-MS) method was developed for the simultaneous quantification of 14 volatile amines in air. The method includes collection of compounds into two midget impingers in a row filled with 15 ml of ultrapure water. The analytical performances with mass spectrometry detection were compared to those obtained with classical conductivity detection. The use of mass spectrometry detection (in SIM mode) overcomes most of the coelutions encountered with conductivity detection. Although the linearity domain of calibrations is reduced for the MS detection as compared with the CD detection, the detection limits in MS detection are highly lowered allowing the quantification of amines at the levels of μg m(-3) in air with a good accuracy for most compounds (RSD of less than 10%). This method was successfully applied to the analysis of amines released from polyurethane foams. Seven amines were identified and some in high concentrations, like dimethylaminoethanol, NIAX and TEDA.     

Characterising sources and sinks of rural VOC in eastern France

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.     

Quantitative cancer risk assessment and local mortality burden for ambient air pollution in an eastern Mediterranean City

Health risks posed by ambient air pollutants to the urban Lebanese population have not been well characterized. The aim of this study is to assess cancer risk and mortality burden of non-methane hydrocarbons (NMHCs) and particulates (PM) based on two field-sampling campaigns conducted during summer and winter seasons in Beirut. Seventy NMHCs were analyzed by TD-GC-FID. PM_2.5 elemental carbon (EC) components were examined using a Lab OC-EC aerosol Analyzer, and polycyclic aromatic hydrocarbons were analyzed by GC-MS. The US EPA fraction-based approach was used to assess non-cancer hazard and cancer risk for the hydrocarbon mixture, and the UK Committee on Medical Effects of Air Pollutants (COMEAP) guidelines were followed to determine the PM_2.5 attributable mortality burden. The average cumulative cancer risk exceeded the US EPA acceptable level (10⁻⁶) by 40-fold in the summer and 30-fold in the winter. Benzene was found to be the highest contributor to cancer risk (39–43%), followed by 1,3-butadiene (25–29%), both originating from traffic gasoline evaporation and combustion. The EC attributable average mortality fraction was 7.8–10%, while the average attributable number of deaths (AD) and years of life lost (YLL) were found to be 257–327 and 3086–3923, respectively. Our findings provide a baseline for future air monitoring programs, and for interventions aiming at reducing cancer risk in this population.

     

VOC in an urban and industrial harbor on the French North Sea coast during two contrasted meteorological situations

Two measurement campaigns of volatile organic compounds (VOC) were carried out in the industrial city of Dunkerque, using Radiello passive samplers during winter (16–23 January) and summer (6–13 June) 2007. 174 compounds were identified belonging to six chemical families. Classifying sampling sites with similar chemical profiles by hierarchical ascending classification resulted in 4 groups that reflected the influence of the main industrial and urban sources of pollution. Also, the BTEX (Benzene, Toluene, Ethylbenzene and Xylenes) quantification allowed us to map their levels of concentration. Benzene and toluene (BT) showed high concentrations in Northern Dunkerque reflecting the influence of two industrial plants. Differences among spatial distributions of the BT concentrations over contrasted meteorological conditions were also observed. An atypical ratio of T/B in the summer samples led us to investigate the BTEX origins shedding light on the contribution of pollutants transported across various zones of VOC emissions situated in Europe.     

Speciation of non-methane hydrocarbons (NMHCs) from anthropogenic sources in Beirut,Lebanon

The chemical composition of emissions from the different anthropogenic sources of non-methane hydrocarbons (NMHC) is essential for modeling and source apportionment studies. The speciated profiles of major NMHC sources in Lebanon, including road transport, gasoline vapor, power generation, and solvent use were established. Field sampling have been carried out by canisters in 2012. Around 67 NMHC (C2 to C9) were identified and quantified by using a gas chromatograph equipped with a flame ionization detector. Typical features of the roadway emissions included high percentages of isopentane, butane, toluene, xylenes, ethylene, and ethyne. Gasoline evaporation profiles included high percentage of the C4–C5 saturated hydrocarbons reaching 59 %. The main compounds of the power generator emissions are related to combustion. Toluene and C8–C9 aromatics were the most abundant species in emissions from paint applications. Finally, the impact of the use of region-specific source profile is tackled regarding the implication on air quality.     

Long term measurement and source apportionment of non-methane hydrocarbons in three French rural areas

Since 1990, the MERA (MEsure des Retombées Atmosphériques, French acronym for background air pollution monitoring) network has been focused on the composition of the lower troposphere within the EMEP program. In particular, 46 non-methane hydrocarbon (NMHC) concentrations have been measured between 1997 and 2006 at three MERA sites.The analysis of temporal trends using Mann-Kendall and Sen methods showed a global decrease of anthropogenic NMHC. These results are in accordance with the trends observed on other sites in Europe and follow the decrease of VOCs emissions in France. Nevertheless the concentrations of long-life species like ethane seem to remain steady showing the growing influence of most distant source areas. In addition isoprene concentrations are typically higher in France than in other countries in Europe and slightly rising. Data analysis was performed using positive matrix factorization (PMF). Five similar PMF factors are identified as aged profiles for the three sites. The examination of factor contributions made it possible to determine a hierarchy in source influence. A higher contribution of evaporative sources was observed on the southern site while residential heating was the main factor for the other two. This work was completed by a clustering analysis (K-means) of air mass trajectories in order to apportion source contribution depending on air mass origins. Two main groups have been distinguished: (1) older and diluted air masses from an oceanic origin; and (2) anthropogenic and closer sources indicating continental influence.