Evaluation of the best compromise between the urban air quality monitoring resolution by diffusive sampling and resource requirements.

The need to collect data representative of overall urban pollution is all-important in order to monitor the population exposure. High spatial resolution monitoring using diffusive samplers allows studying of the urban pollutant distribution, thus enabling deeper investigation of their generation and diffusion mechanisms. Nevertheless, such a monitoring campaign has a certain cost. In this study we point out how to find the best compromise between the number of necessary measurements and the affordable costs for monitoring campaigns. We also describe an innovative method for the proper design of a fixed urban monitoring network by means of preliminary high spatial resolution campaigns using diffusive samplers. Four European capital cities (Dublin, Madrid, Paris and Rome) were monitored six times, each time for seven days. Benzene, toluene, ethylbenzene, xylenes (BTEX) and NO(2) concentrations were measured at 146 sites in Dublin, 293 in Madrid, 339 in Paris and 290 in Rome. Multiscale grids have been drawn which ranged in mesh size from 500 m to 2 km. The statistical processing of data produced a twofold result: the creation of isoconcentration maps with geostatistical procedures, and an algorithm aimed at locating the minimum number of sampling sites where the fixed monitoring stations should be placed. Average urban levels estimated on the basis of these selected sites differ by less than 8% from those calculated on the whole populations of the sampled points. The aim of this work is to investigate how far the resolution of a monitoring campaign of urban pollution by diffusive sampling can be reduced, thus making the monitoring less expensive in terms of human and financial resources, while preserving the same quality of the results that could be achieved with a higher resolution. We found that there is no significant loss of information when the resolution of the monitoring grid for BTEX is lowered to a mesh size of 1.85 km, that is a sampling site each 3.4 km(2), and that the minimum number of sampling sites to be used is N = 0.29 A, where A is the urban surface to be monitored (in km(2)). As the spatial distribution of NO(2) is less sensitive to the distance from the emission source than that of BTEX, this relationship could be retained as a valid lower limit for the mesh grid size also for NO(2) monitoring.

Validation and modelling of a novel diffusive sampler for determining concentrations of volatile organic compounds in air.

A novel diffusive sampler that combines radial and axial diffusion has been developed that improves upon existing commercially available designs. The POcket Diffusive (POD) sampler has been validated under laboratory and field conditions for the measurements of VOCs in ambient air. Laboratory tests varied sampling conditions of temperature (-30-40 C), humidity (10-80%), wind velocity (0.1-4 m s(-1)), and concentration (0.5-50 µg m(-3)) for a number of specific VOCs. An overall uncertainty of circa 9% for the measurement of benzene is calculated for the validation tests, in compliance with the data quality objectives of the EU air quality directive 2008/50/EC. A semi-empirical diffusion model has been developed to estimate sampling rates for compounds that were not tested, and for conditions outside of tested ranges during validation. The diffusion model (and validation tests) shows a low influence of environmental conditions on the sampling rate for the POD sampler. Average reproducibility values of circa 3% are reported with overall sampling uncertainties ranging from 9% to 15%, for the whole range of tested conditions, depending on the compound. The adsorbent cartridge is compatible with existing thermal desorption systems in the market. The diffusive sampler can modify the sampling rate by changing the diffusive body within a range of different porosities. Field tests, conducted in parallel with independent quality controlled canister sampling, confirmed the ease of use and quality of VOC measurements with the POD sampler, for compounds that were, and were not, evaluated during laboratory tests.

Uncertainty models and influence of the calibration span on ambient air measurements of NO2 by chemiluminescence.

An assessment of uncertainty in the hourly and annual limit values of NO 2 measurements by molybdenum NO2-to-NO conversion followed by chemiluminescence detection was carried out at 3 different span concentrations (100, 300 and 700 nmol mol (-1)). The uncertainty of the linearity term was calculated for each span concentration by considering (i) a zero-and-span calibration and (ii) a multipoint calibration. Two uncertainty models were applied for the overall uncertainty estimation: (i) the Standard EN 14211 and (ii) a mechanistic model that considers the NO 2 reduction in the converter. The main difference between these models stems from considering or not the possible covariances derived from interactions between NO x and NO concentrations and the converter's efficiency. For both models, the span determined whether or not it was possible to meet the quality objective requested by the EU Air Quality Directives in the annual limit value when no linearity corrections were performed in environments with NO z/NO2 ratios ≤ 0.04. In environments with significant amounts of NO z species (NOz/NO2≥ 0.12), the expanded uncertainty can easily be higher than the data quality objective if bias' corrections are not or cannot be applied.

Thermal desorption gas chromatography-mass spectrometry as an enhanced method for the quantification of polycyclic aromatic hydrocarbons from ambient air particulate matter.

Polycyclic aromatic hydrocarbons (PAHs) from ambient air particulate matter (PM) were analysed by a two-step thermal desorption (TD) injection system integrated to a gas chromatograph-mass spectrometer (GC/MS). The operational variables of the TD method were optimised and the analytical expanded uncertainties were calculated to vary from 8% to 16% over the operative concentration range (40-4000 pg). The performance of the TD method was validated by the analysis of a standard reference material and by comparison of PAH concentrations in PM samples to those obtained by a conventional liquid extraction (LE) method. The TD method reported lower uncertainties than the LE method for the analysis of similar concentrations in air. The TD method also showed advantages for shorter sampling times in comparison to 24 h for source apportionment applications and for reducing losses of more reactive compounds such as benzo[a]pyrene.

Modelling of the uptake rate of the nitrogen dioxide Palmes diffusive sampler based on the effect of environmental factors.

The influence of environmental parameters on the uptake rate of the nitrogen dioxide (NO(2)) Palmes diffusive sampler was investigated. The main factors affecting the uptake rate were found to be wind speed, the preponderant factor, followed by relative humidity and temperature. The NO(2) concentration and exposure time, as well as the interactions among the factors were not found to have a significant influence on the uptake rate of the Palmes sampler. As a result, a model able to predict the uptake rate of the Palmes sampler was established. In addition, by using the model-predicted uptake rate, the agreement between chemiluminescence and the Palmes sampler during the field tests was improved. The NO(2) Palmes diffusive sampler was shown to comply with the requirement on accuracy defined by the European Directive for the indicative methods of measurements.