Determination of alkylamines in atmospheric aerosol particles: a comparison of gas chromatography–mass spectrometry and ion chromatography approaches

Abstract

Abstract. In recent years low molecular weight alkylamines have been recognized to play an important role in particle formation and growth in the lower atmosphere. However, major uncertainties are associated with their atmospheric processes, sources and sinks, mostly due to the lack of ambient measurements and the difficulties in accurate quantification of alkylamines at trace level. In this study, we present the evaluation and optimization of two analytical approaches, i.e., gas chromatography-mass spectrometry (GC-MS) and ion chromatography (IC), for the determination of alkylamines in aerosol particles. Alkylamines were converted to carbamates through derivatization with isobutyl chloroformate for GC-MS determination. A set of parameters affecting the analytical performances of the GC-MS approach, including reagent amount, reaction time and pH value, was evaluated and optimized. The accuracy is 84.3-99.1 %, and the limits of detection obtained are 1.8-3.9 pg (or 0.02-0.04 ng m −3 ). For the IC approach, a solid-phase extraction (SPE) column was used to separate alkylamines from interfering cations before IC analysis. 1-2 % (v/v) of acetone (or 2-4 % (v/v) of acetonitrile) was added to the eluent to improve the separation of alkylamines on the IC column. The limits of detection obtained are 2.1-15.9 ng (or 0.9-6.4 ng m −3 ), and the accuracy is 55.1-103.4 %. The lower accuracy can be attributed to evaporation losses of amines during the sample concentration procedure. Measurements of ambient aerosol particle samples collected in Hong Kong show that the GC-MS approach is superior to the IC approach for the quantification of primary and secondary alkylamines due to its lower detection limits and higher accuracy.

Large Increases in Primary Trimethylaminium and Secondary Dimethylaminium in Atmospheric Particles Associated With Cyclonic Eddies in the Northwest Pacific Ocean

“…One replicated injection of standards was carried out after running every 10 samples. Note that diethylaminium (DEA + ) may be coeluted with TMA + in the analyses (Huang et al, ; Vandenboer et al, ). However, based on the aforementioned marine biogenic processes and previous field measurements, TMA + very likely overwhelms DEA + in marine atmospheric particles (Carpenter et al, ; Lidbury et al, ; Healy et al, ).…”

Characteristics and sources of aerosol aminiums over the eastern coast of China: insights from the integrated observations in a coastal city, adjacent island and surrounding marginal seas

“…The MMAH + and MEAH + in the aerosols could not be quantified because their peaks were obscured by the wide and distorted peak of NH + 4 . It should be noted that TMAH + and DEAH + could not be completely separated using the IC system (VandenBoer et al, 2011(VandenBoer et al, , 2012Zhou et al, 2018;Huang et al, 2014). Therefore, the sum of TMAH + and DEAH + concentrations (TMDEAH + ) were quantified using the calibration curve of TMAH + with errors less than 3 % .…”

“…Although the lifetime of gaseous amines in the atmosphere is only a few hours, it can be prolonged after amines partition into the particle phase, and thus they may be transported over a long range (Nielsen et al, 2012). Many studies have been done on the gas and/or particle phases of amines over eastern China and adjacent seas (Huang et al, 2012(Huang et al, , 2016Hu et al, 2015;Zheng et al, 2015;Tao et al, 2016;Yu et al, 2016;Shen et al, 2017;Xie et al, 2018;Yao et al, 2016Yao et al, , 2018. For example, C1 to C6 amines over Shanghai were measured during the summer of 2015, of which C1, C2 and C4 amines were the dominant species with average concentrations of 15.7, 40.0 and 15.4 ppt, respectively .…”

Determination of atmospheric amines by on-fiber derivatization solid-phase microextraction with 2,3,4,5,6-pentafluorobenzyl chloroformate and 9-fluorenylmethoxycarbonyl chloride

“…Moreover, sampling can be done from a liquid followed by immersion of the fiber in the derivatization solution or extraction/derivatization of analytes was done with fibers previously coated with reagent [21,22]. Isobutyl chloroformate has been used for the determination of amines extracted from atmospheric aerosols and gas-phase samples by GC-MS [23,24]. However, the procedures are time-consuming, laborious, and costly, including extraction, derivatization with a large volume of solvent and derivatization reagent and, finally, clean-up before the GC-MS analysis.…”