Quantification of trace metalloids and metals in airborne particles applying dynamic reaction cell inductively coupled plasma mass spectrometry.

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.

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.

A case study of personal exposure to nitrogen dioxide using a new high sensitive diffusive sampler.

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.

An automated monitoring system for VOC ozone precursors in ambient air: development, implementation and data analysis.

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.

Validation tests of a new high uptake rate passive sampler for nitrogen dioxide measurements.

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.

Performances and application of a passive sampling method for the simultaneous determination of nitrogen dioxide and sulfur dioxide in ambient air.

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.

Characterisation of NMHCs in a French urban atmosphere: overview of the main sources.

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.

Multi-element analysis by inductively coupled plasma optical emission spectrometry of airborne particulate matter collected with a low-pressure cascade impactor.

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.