Deployment of a ground-based CIMS apparatus for the detection of organic gases in the boreal forest during the QUEST campaign

Abstract

Abstract. Measurements of atmospheric volatile organic compounds were performed in the Finnish Boreal forest atmosphere during spring 2003, as part of the project QUEST (Quantification of Aerosol Nucleation in the European Boundary Layer), using a ground-based Chemical Ionization Mass Spectrometer (CIMS) instrument. Based on the study of their hydrate distribution, methanol, acetonitrile, acetaldehyde, dimethyl amine (DMA), ethanol/formic acid, acetone, trimethyl amine (TMA), propanol/acetic acid, isoprene, methyl vinyl ketone (MVK) and metacrolein (MaCR), monoterpenes and monoterpene oxidation product (MTOP) are proposed as candidates for masses 32, 41, 44, 45, 46, 58, 59, 60, 68, 70, 136, and 168 amu, respectively. It would be, to our knowledge, the first time DMA, TMA and MTOP are measured with this method. Most compounds show a clear diurnal variation with a maximum in the early night, corresponding to the onset of the noctural inversion and in agreement with independant measurements of CO. Biogenic compounds are highly correlated with each other and the ratio monoterpene/oxidation product shows a typical daily pattern of nightime maxima. However, because isoprene mixing ratios are also maximum during the early night, it is likely that it suffers of the interference from another unidentified biogenic compound. Hence mass 68 amu is identified as isoprene+compound X.

Geographical and diurnal features of amine‐enhanced boundary layer nucleation

“…The partitioning of gas phase amines to the particle phase is complex due to the large number of chemical species and reactions involved. Several studies [Ge et al, 2011] have suggested that amines produce SOA by dissolving directly into acidic particles in high RH [Sellegri et al, 2005;Rehbein et al, 2011] and subsequently reacting with acidic compounds within the particles and producing salts [e.g., Spencer et al, 2007; Journal of Geophysical Research: Atmospheres 10.1002/2015JD023181 Facchini et al, 2008;Smith et al, 2010;Williams et al, 2010]. With a plethora of research related to how amines partition to the particulate phase through different mechanisms, such as the oxidation of amine precursors [Silva et al, 2008;Malloy et al, 2009], amide products [Zahardis et al, 2008], ozonolysis of amines [Erupe et al, 2010], and acid-base reactions [Spencer et al, 2007;Facchini et al, 2008;Sorooshian et al, 2009;Williams et al, 2010;Smith et al, 2010], the pathway of amines to particles remains an open question.…”

“…This lack of understanding limits the development of NPF parameterizations that are able to account for temporal and spatial characteristics of aerosol formation and growth as well as subsequent impacts on climate. Recently, for example, organic and alkaline molecules have been suggested to participate in nucleation, and especially the role of amines in new particle formation has attracted increasing attention involving laboratory [ Barsanti et al , ; Huang et al , ; Berndt et al , ; Erupe et al , ; Kirkby et al , ; Chen et al , ; Almeida et al , ; Jen et al , ; Glasoe et al , ] and ambient measurements [ Sellegri et al , ; Murphy et al , ; Malloy et al , ; Smith et al , ; Hanson et al , ; Kulmala et al , ] as well as quantum mechanical [ Kurtén and Vehkamäki , ; Kurtén et al , ; Loukonen et al , ; McGrath et al , ; Ortega et al , ; Olenius et al , ] and other modeling studies [ Myriokefalitakis et al , ; Paasonen et al , ; Yli‐Juuti et al , ; Yu and Luo , ]. The experimental observations by Almeida et al [] showed that the enhancement of NPF by dimethylamine can be 1000‐fold stronger than by ammonia.…”

Calibration and intercomparison of acetic acid measurements using proton-transfer-reaction mass spectrometry (PTR-MS)

“…Although acetic acid has been measured previously via PTR-MS and related MS techniques (Lindinger et al, 1998b;Holzinger et al, 2000;Williams et al, 2001;Warneke et al, 2004;Karl et al, 2004Karl et al, , 2005Jobson et al, 2005;Sellegri et al, 2005;de Gouw et al, 2006;Feilberg et al, 2010), few studies report results based on direct instrumental calibration. Lee et al (2006b) calibrated their instrument by diluting pure acetic acid into a Teflon bag with purified air.…”

Denuder sampling techniques for the determination of gas-phase carbonyl compounds: A comparison and characterisation of in situ and ex situ derivatisation methods

“…Furthermore, such on-line techniques utilising specific ionisation techniques prior to mass spectrometric (MS) detection have also been applied for carbonyl compound measurements. Those techniques are atmospheric pressure chemical ionisation MS (APCI-MS) [28], selected ion flow tube MS (SIFT-MS) [29,30], chemical ionisation MS (CIMS) [31] and proton transfer reaction MS (PTR-MS) [32,33]. On-line MS techniques require no complicated sample preparation procedures but difficulties need to be accounted for the ionisation efficiency of unknown compounds or isobaric isomers which cannot be separated (i.e.…”