Size distribution of alkyl amines in continental particulate matter and their online detection in the gas and particle phase

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Abstract

An ion chromatographic method is described for the quantification of the simple alkyl amines: methylamine (MA), dimethylamine (DMA), trimethylamine (TMA), ethylamine (EA), diethylamine (DEA) and triethylamine (TEA), in the ambient atmosphere. Limits of detection (3Ï) are in the tens of pmol range for all of these amines, and good resolution is achieved for all compounds except for TMA and DEA. The technique was applied to the analysis of time-integrated samples collected using a micro-orifice uniform deposition impactor (MOUDI) with ten stages for size resolution of particles with aerodynamic diameters between 56 nm and 18 Î1/4m. In eight samples from urban and rural continental airmasses, the mass loading of amines consistently maximized on the stage corresponding to particles with aerodynamic diameters between 320 and 560 nm. The molar ratio of amines to ammonium (R3NH+/NH4+) in fine aerosol ranged between 0.005 and 0.2, and maximized for the smallest particle sizes. The size-dependence of the R3NH+/NH4+ ratio indicates differences in the relative importance of the processes leading to the incorporation of amines and ammonia into secondary particles. The technique was also used to make simultaneous hourly online measurements of amines in the gas phase and in fine particulate matter using an Ambient Ion Monitor Ion Chromatograph (AIM-IC). During a ten day campaign in downtown Toronto, DMA, TMA + DEA, and TEA were observed to range from below detection limit to 2.7 ppt in the gas phase. In the particle phase, MAH+ and TMAH+ + DEAH+ were observed to range from below detection limit up to 15 ng mĝ̂'3. The presence of detectable levels of amines in the particle phase corresponded to periods with higher relative humidity and higher mass loadings of nitrate. While the hourly measurements made using the AIM-IC provide data that can be used to evaluate the application of gas-particle partitioning models to amines, the strong size-dependence of the R3NH+/NH4+ ratio indicates that using bulk measurements may not be appropriate. © 2011 Author(s).

Figures

  • Fig. 1. Sample CS17 chrom togra of p rticles collected on the 440±120 nm MOUDI stage at Dorset, ON. Peaks are: 1 – sodium, 2 – ammonium, 3 – potassium, 4 – dimethylamine, 5 – trimethlyamine and diethylamine, 6 – triethylamine, 7 – magnesium, 8 – calcium.
  • Fig. 2. Chromatograms of particles collected on the 780±200 nm MOUDI stage at Lambton Shores, ON separated on (A) CS12A and (B) CS17 columns. Compounds are: 1 – sodium, 2 – ammonium, 3 – potassium, 4 – dimethylamine, 5 – trimethylamine and diethylamine, 6 – magnesium, 7 – calcium.
  • Table 1. MOUDI size-resolved particulate matter sample collection and analysis information. Eight samples were collected over the course of a year using either a rotating or fixed set of MOUDI stages. Mass loadings of PM1.8 amines in the particulate MOUDI samples are reported and then calculated as a function of measureable water soluble mass (msol), total mass (mtot), as well as relative to PM1.8 NH + 4 .
  • Table 2. The maximum mass loading (ng m−3) on a single stage, for each amine species quantified in the MOUDI sample. The median diameter (nm) of the size bin where each species maximizes is given in parentheses when it is not the 320–560 nm size bin. No amines were consistently detected in all size bins from 0.056 to 18 µm, so a range was not reported as the lower value would always be below the limit of detection. ND indicates the species was not detected on any stage of the MOUDI.
  • Fig. 3. Mole equivalent distribution of major water-soluble ions in MOUDI samples. (A) Sample 4 collected in Dorset, (B) Sample 3 collec ed in Toronto (C) Sample 8 collected in Lambton Shores.
  • Fig. 4. Amine mass distributions as a function f particle diameter for (A) Sample 4 collected in Dorset, (B) Sample 3 collected in Toronto (C) Sample 8 collected in Lambton Shores, and (D) Sample 1 collected in Toronto.
  • Fig. 5. Ratio of the sum of all particulate amines (R3NH+) measured to the total ammonium (moles/moles) as a function of particle dia eter for (A) Sample 4 collected in Dorset, (B) Sample 3 collected in Toronto (C) Sample 8 collected in Lambton Shores, and (D) Sample 1 collected in Toronto.
  • Fig. 6. Online AIM-IC observations of amines and dominant inorganic constituents in (A) the gas phase and (B) PM2.5. In each panel, the left axis applies to amines, and the right axis to inorganic consituents. Detection limits for amines are depicted using dashed lines.

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APA

Vandenboer, T. C., Petroff, A., Markovic, M. Z., & Murphy, J. G. (2011). Size distribution of alkyl amines in continental particulate matter and their online detection in the gas and particle phase. Atmospheric Chemistry and Physics, 11(9), 4319–4332. https://doi.org/10.5194/acp-11-4319-2011

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