Towards an Optical Gas Standard for Traceable Calibration-Free and Direct NO2 Concentration Measurements

Abstract

We report a direct tunable diode laser absorption spectroscopy (dTDLAS) instrument developed for NO2 concentration measurements without chemical pre-conversion, operated as an Optical Gas Standard (OGS). An OGS is a dTDLAS instrument that can deliver gas species amount fractions (concentrations), without any previous or routine calibration, which are directly traceable to the international system of units (SI). Here, we report NO2 amount fraction quantification in the range of 100–1000 µmol/mol to demonstrate the current capability of the instrument as an OGS for car exhaust gas application. Nitrogen dioxide amount fraction results delivered by the instrument are in good agreement with certified values of reference gas mixtures, validating the capability of the dTDLAS-OGS for calibration-free NO2 measurements. As opposed to the standard reference method (SRM) based on chemiluminescence detection (CLD) where NO2 is indirectly measured after conversion to NO, titration with O3 and the detection of the resulting fluorescence, a dTDLAS-OGS instrument has the benefit of directly measuring NO2 without distorting or delaying conversion processes. Therefore, it complements the SRM and can perform fast and traceable measurements, and side-by-side calibrations of other NO2 gas analyzers operating in the field. The relative standard uncertainty of the NO2 results reported in this paper is 5.1% (k = 1, which is dominated (98%) by the NO2 line strength), the repeatability of the results at 982.6 µmol/mol is 0.1%, the response time of the instrument is 0.5 s, and the detection limit is 825 nmol/mol at a time resolution of 86 s.