Assessment of uncertainty of NO2 measurements by the chemiluminescence method and discussion of the quality objective of the NO2 European Directive

Abstract

Hereafter, an assessment of the ability of the chemiluminescence method to measure ambient NO₂ with an accuracy within 15%, as requested by the data quality objective of European directive 1999/30/CE, is presented. In general, uncertainty is evaluated using the response to reference materials or by means of inter-comparisons used to determine some statistics like repeatability, reproducibility and calibration bias. These are incomplete approaches and the method of the Guide to the Expression of Uncertainty in Measurement, advised by the Directive, should be preferred. In fact, even if it requires a large data set, it allows the relative influence of all possible sources of uncertainty to be studied. The extent of NO₂ uncertainty is mainly dependent on the level of NO. It is decreased by NOx and the correlation between NOx and NO. Furthermore, the uncertainty budget reveals that the contribution of accuracy of calibration standard, linearity, converter efficiency and drift of the analyser between calibration checks to the overall uncertainty is less important than the contribution of interference, mainly humidity and PAN in rural areas. The relative expanded uncertainty of the NO₂ hourly average exceeds 30% for NO₂ concentrations lower than 40 µg m⁻³. Nevertheless, the data quality objective of 15% is reached for 200 µg m⁻³, the hourly limit value of the European directive. On the contrary, at the limit value on the annual average, 40 µg m⁻³, the data quality objective is not met if NO is higher than 100 µg m⁻³. However, the data quality objective could be reached by correcting the measurements with the bias due to interference.