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Novel traceable analytical methods and reference gas standards were developed for the detection of trace-level ammonia in biogas and biomethane. This work focused on an ammonia amount fraction at an upper limit level of 10 mg m -3 (corresponding to approximately 14 μmol mol -1 ) specified in EN 16723-1:2016. The application of spectroscopic analytical methods, such as Fourier transform infrared spectroscopy, cavity ring-down spectroscopy, and optical feedback cavity-enhanced absorption spectroscopy, was investigated. These techniques all exhibited the necessary ammonia sensitivity at the required 14 μmol mol -1 amount fraction. A 29-month stability study of reference gas mixtures of 10 μmol mol -1 ammonia in methane and synthetic biogas is also reported.

The first reference gas mixtures of sulfur-free natural gas odorants that are traceable to the International System of Units (SI) have been produced and their compositions validated. These mixtures, which contain methyl acrylate and ethyl acrylate at amount fractions between 1.1 and 2.1 μmol mol(-1), can be used to underpin measurements of sulfur-free odorants, which are increasingly being used to odorize natural gas in transmission networks as they have less harmful properties than traditional sulfur-containing odorants. The reference gas mixtures produced have been shown to be stable in passivated aluminum cylinders for at least 8 months and have been validated (to within 6% or less) by interlaboratory measurements at three National Measurement Institutes. The stability of methyl acrylate and ethyl acrylate in gas sampling bags has been investigated, and the challenges of analyzing 2-ethyl-3-methylpyrazine, which is used as a stabilizer in sulfur-free odorants, are also briefly discussed.