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A novel sampler for aliphatic amines and a new method for determination using hydrophilic interaction liquid chromatography tandem mass spectrometry
Stockholm University, Faculty of Science, Department of Analytical Chemistry.
Stockholm University, Faculty of Science, Department of Analytical Chemistry.
Stockholm University, Faculty of Science, Department of Analytical Chemistry.
Stockholm University, Faculty of Science, Department of Analytical Chemistry.
(English)Manuscript (preprint) (Other academic)
Abstract [en]

A novel sampler for determination of airborne aliphatic amines is presented using hydrophilic interaction liquid chromatography (HILIC) with tandem mass spectrometry (MSMS). The sampler consisted of a denuder comprising a polypropylene tube (length = 7 cm, ID = 0.8 cm) with an inner wall coated with a glass fibre filter and internal glass fibre filter strip folded into a ‘V’ to increase the denuder surface coupled in series with a 13 mm glass fibre filter. Sulphuric acid was used for impregnation of all the filters.

Electrospray ionisation and multiple-reaction monitoring (MRM) of the protonated molecular ions and corresponding deuterium-labelled internal standards resulted in selective determination with linear correlation coefficients > 0.995,  instrumental precision (n = 16) < 6 %  and detection limits of 1.9 - 150 pg (2.6 - 195 ng mL-1) for ethylamine (EA), allylamine (AA), isopropanol amine (IPA), n-butylamine (NBA), diethylamine (DEA), dimethylethylamine (DMEA), cyclohexylamine (CHA), diisopropylamine (DIPA) and triethylamine (TEA).

The performance of the sampler was investigated by sampling a standard atmosphere of AA, IPA, NBA, DEA, DMEA, CHA and TEA (0.5-15.4 mg m-3) in an exposure chamber (0.3 m3). The air concentrations of the amines were generated by gas phase membrane permeation.

The extraction recovery for spiked samplers (10-100 μg) was in the range 93-106 % (except for DMEA 127 %). The precision when sampling three series of ten samplers each was in the range 1.8-7.0 %. Collection efficiencies of > 99.9 % without breakthrough were observed for the studied amines when sampling over 60 min using four sets of two samplers in sequence at a flow rate of 200 mL min-1. Major breakthrough was observed for TEA and DMEA at 800 mL min-1 with collection efficiencies > 82 %. For CHA, DEA, NBA, IPA and AA, the collection efficiencies were > 97 %. The distribution of the aliphatic amines in the sampler was studied by dissection of the denuders (into eight parts) for two different flow rates (200 and 1100 mL min-1). The first parts of the denuder collected the highest amount of aliphatic amines, which then declined throughout the remaining parts. Thus, it was deemed that the denuder was too short to collect all gas phase amines and the presence of the end filter was necessary for efficient collection. No effect was observed on the collection efficiency when samplers were stored for up to 45 days prior to sampling. No degradation of the amines on the sampler was observed when exposed samplers were stored for up to 45 days. When sampling IPA, DEA and TEA over a period of 0.5 - 8 h (n = 6), linear relationships were obtained with correlation coefficients > 0.997. Using sampling flow rates of 50-800 mL min−1, linear relationships were obtained with correlation coefficients > 0.977. Pre- or post-exposure to ambient air for up to 10 h at 25 °C or 50 °C did not affect the sampler performance.

Keyword [en]
Aliphatic amines, Hydrophilic Interaction Liquid Chromatography, HILIC, dry sampling, liquid chromatography–mass spectrometry, Denuder, filter, sampler
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
URN: urn:nbn:se:su:diva-93921OAI: oai:DiVA.org:su-93921DiVA: diva2:651121
Available from: 2013-09-24 Created: 2013-09-19 Last updated: 2014-01-23
In thesis
1. Isocyanates, Amines and Alkanolamines: Sampling, Chromatography and Detection
Open this publication in new window or tab >>Isocyanates, Amines and Alkanolamines: Sampling, Chromatography and Detection
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Isocyanates, aromatic-, aliphatic- and alkanolamines are commonly used in the industry today. Millions of workers in Europe are exposed. The most frequent health symptoms are respiratory and dermal disorder. Due to the health risk most of the compounds in this thesis are regulated by authorities and have occupational exposure limits (OELs). Consequently, reliable and robust air sampling methods are urgently needed.

In this thesis dry samplers for isocyanates, aliphatic- and alkanolamines have been developed and evaluated. The isocyanate sampler is now a commercial product (ASSET EZ4-NCP Dry Sampler, Supelco). The samplers were based on a denuder with a filter in series. The denuder and filter were impregnated with di-n-butylamine for the isocyanate sampler and with sulphuric acid for the aliphatic- and alkanolamine sampler.

The robustness of the dry samplers was extensively evaluated. This was performed in a climate chamber containing a controlled atmosphere of the studied compounds.

New methods based on hydrophilic interaction liquid chromatography (HILIC) coupled with tandem mass spectrometry (MSMS) were developed for determination of aromatic-, aliphatic- and alkanolamines in aqueous solutions. Isocyanates were determined by reversed-phase liquid chromatography MSMS.

HILIC in combination with MS is a most powerful system, and highly sensitive determinations, several orders of magnitude below the OELs, of polar compounds present in the work environment can be accomplished.

The selected samplers enable sampling during short sampling times and for whole work shifts. The samplers can be stored for months before and after sampling. The performance of the samplers was unaffected by variation in temperature, humidity, flow-rate and pre- and post-sampling of ambient air.

Sampling for the compounds studied is now greatly simplified, and assessment of the work environment is facilitated.

Place, publisher, year, edition, pages
Stockholm: Department of Analytical Chemistry, Stockholm University, 2013. 114 p.
Keyword
Air-sampling, Isocyanates, Aromatic amines, Aliphatic amines, Alkanolamines, Hydrophilic Interaction Liquid Chromatography, Dry Denuder-Filter sampler, Liquid Chromatography–tandem Mass Spectrometry, Polyurethane Foam Extraction
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-94067 (URN)978-91-7447-747-4 (ISBN)
Public defence
2013-11-01, Vita Salen, Hässleholms Kulturhus, Vattugatan 18/Järnvägsgatan 23, Hässleholm, 13:00 (Swedish)
Opponent
Supervisors
Note

At the time of the doctoral defence the following papers were unpublished and had a status as follows: Paper 1: Epub ahead of print; Papers 3-5: Manuscripts

Available from: 2013-10-10 Created: 2013-09-24 Last updated: 2014-02-12Bibliographically approved

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