Sampling and analytical methodology development for the determination of primary and secondary low molecular weight amines in ambient air

Abstract

In this project, a sampling device and an analytical method have been developed to simultaneously analyse the most frequently found low molecular weight amines, including aliphatic, aromatic and alcohol amines. These amines are diethanolamine, ethanolamine, methylamine, isopropylamine, morpholine, dimethylamine, and aniline. A sampling device was developed using a 37 mm cassette with glass fibre filters impregnated with sulfuric acid. Immediately after sampling, the filter was transferred to vials containing a solution of dansyl chloride. Dansyl chloride was used for derivatisation because it forms aromatic sulfonamides that are fluorescent and easy to protonate for MS detection. The effect of using an internal standard made with the dansylated derivative of 1-(2-methoxyphenyl)piperazine (MOPIP) on the uncertainty and efficiency of the method was also evaluated. This internal standard was spiked directly onto filters. The coupling of HPLC/ESI-MS was used for the simultaneous analysis of all the derivatives. This method showed detection limits of about 0.03 microg mL(-1) to 0.3 microg mL(-1) of amine with an average expanded uncertainty of 3% to 6% depending on the amine. The methodology recoveries are close to 100% for all the amines, and the overall estimated expanded uncertainties vary between 10% and 13% depending on the amine. This new strategy will be useful in evaluating workplace air since a unique sampling system will be used, independent of the amine to be quantified.

Measurement of gas-phase ammonia and amines in air by collection onto an ion exchange resin and analysis by ion chromatography

“…6, which are a measure of the precision of this technique and are 2-15 % for ammonia, MA, DMA and TMA. These values are similar to those obtained for other techniques that have used gas-phase amine standards for characterization (Fournier et al, 2008). In addition, they likely represent an upper limit to the error associated with this technique as the system used to generate the gas-phase standards (Fig.…”

“…On-line mass spectrometric (MS) techniques include ambient pressure proton transfer MS (Hanson et al, 2011), chemical ionization MS , and proton transfer reaction MS (PTR-MS) (Borduas et al, 2013;Feilberg et al, 2010;Kuhn et al, 2011;Liu et al, 2011;Tanimoto et al, 2007). Off-line techniques typically involve collection of a gas-phase sample onto a substrate (e.g., activated charcoal or an acid-impregnated glass fiber filter) (Fournier et al, 2008;Fuselli et al, 1982), into an acidic solution (Akyüz, 2008;Gronberg et al, 1992;Schade and Crutzen, 1995), or onto a whetted glass frit (Huang et al, 2009). Samples are then extracted and analyzed using gas or liquid chromatography, sometimes with a derivatization step included (Akyüz, 2008;Fuselli et al, 1982;Gronberg et al, 1992;Hiranuma et al, 2010;Huang et al, 2009;Nishikawa and Kuwata, 1984;Santagati et al, 2002;Schade and Crutzen, 1995).…”

Quantitation of 11 alkylamines in atmospheric samples: separating structural isomers by ion chromatography

“…From these works, alkylamines have been shown to form clusters via neutralization reactions at rates up to 3 orders of magnitude greater than ammonia (Almeida et al, 2013;Berndt et al, 2010;Bzdek et al, 2011;Kurtén et al, 2008;Loukonen et al, 2010;Nadykto et al, 2015) and readily exchange with ammonium in ammonium-bisulfate molecular clusters (Bzdek et al, 2010;Lloyd et al, 2009;Qiu et al, 2011). These studies suggest that alkylamines can compete with ammonia to form particles even though they have been quantified at mixing ratios that are 3 or more orders of magnitude lower in the atmosphere (Chang et al, 2003;Ge et al, 2011;Schade and Crutzen, 1995). Atmospheric measurements made during new particle formation events have further confirmed that alkylamines participate in particle formation at ambient concentrations and that these species may be present in most atmospheric particles (Creamean et al, 2011;Dall'Osto et al, 2012;Hodshire et al, 2016;Kulmala et al, 2013;Kürten et al, 2016;Ruiz-Jimenez et al, 2012;Smith et al, 2010;Tao et al, 2015).…”

Study of OH-initiated degradation of 2-aminoethanol

“…Initial mixing ratio of TMB in E1 and E2 was about 200 ppbv. MEA was injected with a Harvard 22 syringe pump system with air stream heating (Fournier et al, 2008; with modifications) which allows for transfer of a known amount of MEA into the chamber. However, MEA losses during injection which occur between the outlet of the syringe and the inlet of the chamber can be substantial and it was not possible to quantify the lost amount.…”