Laboratoire Interuniversitaire des Systèmes Atmosphériques (LISA), UMR-CNRS 7583, Université Paris-Est-Créteil (UPEC) et
Université Paris Diderot (UPD), Paris, France
Received: 05 Oct 2016 – Discussion started: 07 Nov 2016
Abstract. A commercial PTR-TOF-MS has been optimized in order to allow the measurement of individual organic nitrates in the atmosphere. This has been accomplished by shifting the distribution between different ionizing analytes, H3O+∕ H3O+(H2O)n or NO+∕ NO2+. The proposed approach has been proven to be appropriate for the online detection of individual alkyl nitrates and functionalized nitrates. It has been shown that hydroxyl and ketonitrates have a high affinity towards NO+, leading to the formation of an adduct that allows the easy identification of the organic nitrate (R) from the R–NO+ ion signal. The recorded sensitivities for both ionization modes correspond to detection limits of tens of ppt min−1 in the case of hydroxy- and ketonitrates. Alkyl nitrates exhibit a moderate affinity towards NO+ ionization leading to detection units of few hundreds of ppt and the highest sensitivity in H3O+ mode was obtained for the water adducts signals. However, this method exhibits much lower capabilities for the detection of peroxyacetyl nitrates with detection limits in the ppb range.
Revised: 31 Jan 2017 – Accepted: 02 Mar 2017 – Published: 18 Apr 2017
Duncianu, M., David, M., Kartigueyane, S., Cirtog, M., Doussin, J.-F., and Picquet-Varrault, B.: Measurement of alkyl and multifunctional organic nitrates by proton-transfer-reaction mass spectrometry, Atmos. Meas. Tech., 10, 1445-1463, doi:10.5194/amt-10-1445-2017, 2017.