Ambient measurements of aromatic and oxidized VOCs by PTR-MS and GC-MS: intercomparison between four instruments in a boreal forest in Finland

Abstract

Abstract. Proton transfer reaction mass spectrometry (PTR-MS) and gas chromatography mass spectrometry GC-MS) allow real-time measurements of various atmospheric volatile organic compounds (VOC). By taking parallel measurements in ambient conditions, two PTR-MSs and two GC-MSs were studied for their ability to measure methanol, acetaldehyde, acetone, benzene and toluene. The measurements were conducted at a rural boreal forest site in southern Finland between 13 April and 14 May 2012. This paper presents correlations and possible biases between the concentrations measured using the four instruments. This paper presents correlations and possible biases between the concentrations measured using the four instruments. A very good correlation was found for benzene and acetone measurements between all instruments (the mean R value was 0.88 for both compounds), while for acetaldehyde and toluene the correlation was weaker (with a mean R value of 0.50 and 0.62, respectively). For some compounds, notably for methane, there were considerable systematic differences in the mixing ratios measured by the different instruments, despite the very good correlation between the instruments (mean R = 0.90). The systematic difference arises as a difference in the linear regression slope between measurements conducted between instruments, rather than as an offset. This mismatch indicates that the systematic uncertainty in the sensitivity of a given instrument can lead to an uncertainty of 50–100% in the methanol emissions measured by commonly used methods.