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The performance of 18 European institutions involved in long-term non-methane hydrocarbon (NMHC) measurements in ambient air within the framework of the Global Atmosphere Watch (GAW) and the European Monitoring and Evaluation Programme (EMEP) was assessed with respect to data quality objectives (DQOs) of ACTRIS (Aerosols, Clouds, and Trace gases Research InfraStructure Network) and GAW. Compared to previous intercomparison studies the DQOs define a novel approach to assess and ensure a high quality of the measurements. Having already been adopted by GAW, the ACTRIS DQOs are demanding with deviations to a reference value of less than 5% and a repeatability of better than 2% for NMHC mole fractions above 0.1 nmol mol(-1). The participants of the intercomparison analysed two dry gas mixtures in pressurised cylinders, a 30-component NMHC mixture in nitrogen (NMHC_N-2 /at approximately 1 nmol mol(-1) and a whole air sample (NMHC_air), following a standardised operation procedure including zero-and calibration gas measurements. Furthermore, participants had to report details on their instruments and assess their measurement uncertainties. The NMHCs were analysed either by gas chromatography-flame ionisation detection (GC-FID) or by gas chromatography-mass spectrometry (GC-MS). For the NMHC_N-2 measurements, 62% of the reported values were within the 5% deviation class corresponding to the ACTRIS DQOs. For NMHC_air, generally more frequent and larger deviations to the assigned values were observed, with 50% of the reported values within the 5% deviation class. Important contributors to the poorer performance in NMHC_air compared to NMHC_N-2 were a more complex matrix and a larger span of NMHC mole fractions (0.03-2.5 nmol mol(-1)). The performance of the participating laboratories were affected by the different measurement procedures such as the usage of a two-step vs. a one-step calibration, breakthroughs of C-2-C-3 hydrocarbons in the focussing trap, blank values in zero

Proton transfer reaction mass spectrometry (PTR-MS) and gas chromatography mass spectrometry GC-MS) are commonly used methods for automated in situ measurements of various volatile organic compounds (VOCs) in the atmosphere. In order to investigate the reliability of such measurements, we operated four automated analyzers using their normal field measurement protocol side by side at a boreal forest site. We measured methanol, acetaldehyde, acetone, benzene and toluene by two PTR-MS and two GC-MS instruments. The measurements were conducted in southern Finland between 13 April and 14 May 2012. This paper presents correlations and 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 methanol, 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 manifests 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.