Abstract
Atmospheric amines are ubiquitous compounds in the atmosphere, having both natural and anthropogenic origin. Recently, they have been identified as important contributors to new particle formation in the atmosphere, but observations of their atmospheric concentrations are scarce. In the present study we introduce the first systematic long-term observations of gas-phase amines measurements in the East Mediterranean atmosphere. Air samples were collected at the Finokalia monitoring station of the University of Crete during a 3.5-year period from January 2013 to July 2016, and analyzed after extraction using a high-performance liquid chromatography triple quadrupole mass spectrometer. The detected alkylamines were the sum of dimethylamine and ethylamine (DMA+EA), trimethylamine (TMA), diethylamine (DEA) and triethylamine (TEA). DMA+EA and TMA were the most abundant alkylamines, with concentrations spanning from the detection limit to 78.0 and 69.8 pptv, and average concentrations of 7.8 ± 12.1 and 7.5 ± 12.4 pptv, respectively. Amines showed pronounced seasonal variability with DMA+EA and TMA concentrations being higher in winter. Statistical analysis of the observations showed different sources for each of the studied amines, except for DMA+ΕA and DEA that appear to have common sources in the region. This analysis points to a marine source of TMA and animal husbandry in the area as a potential source of TEA. None of the alkylamines is correlated with other anthropogenic sources. Furthermore, no clear association was found between the seasonality of NPF events and alkylamines concentrations, while a clear correlation was detected between the seasonality of nucleation mode particle (dp < 25 nm) number concentrations and alkylamine concentrations, indicating that amines may contribute to nucleation mode particles’ production.
Highlights
Alkylamines are derivatives of ammonia, where H atoms are replaced by alkyl (R) structures and can be distinguished in primary (RNH2), secondary (R2NH) and tertiary (R3N) amines
Alkylamines participate in aerosol formation contributing to new particle formation (NPF) and growth [14,15,16,17,18,19]
Simultaneous submicron aerosol size distribution measurements with a scanning mobility particle sizer (SMPS) analyzer [43] enabled the investigation of NPF events and their seasonality in the East Mediterranean
Summary
Alkylamines are derivatives of ammonia, where H atoms are replaced by alkyl (R) structures and can be distinguished in primary (RNH2), secondary (R2NH) and tertiary (R3N) amines. Alkylamines participate in aerosol formation contributing to new particle formation (NPF) and growth [14,15,16,17,18,19] Because of their higher basicity, amines are likely to bind to sulfuric acid more efficiently than ammonia. Mean concentrations of DMA < 0.15 pptv [34], TMA ~1 pptv [30,39], DEA 0.3 and TEA 0.1 pptv [25] were measured These reported differences in the mixing ratios of amines reflect source and sink variability, and differences in the sampling and analytical methods. Simultaneous submicron aerosol size distribution measurements with a scanning mobility particle sizer (SMPS) analyzer [43] enabled the investigation of NPF events and their seasonality in the East Mediterranean
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