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Analysis of Aqueous Alkanolamines using Hydrophilic Interaction Liquid Chromatography and Mass Spectrometr
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.
2013 (English)In: Analytical Chemistry Letters, ISSN 2229-7928, Vol. 3, no 5-6, 298-313 p.Article in journal (Refereed) Published
Abstract [en]

A method for determination of mono-, di-, triethanolamine (EA, DEA, TEA), iso-, N-propanolamine (IPA, NPA),  diisopropyl ethanol amine (DIPEA), 2-diethylethanol amine (DEEA), diisopropanol amine (DIPA), dimethylethanol amine (DMEA), N-methyldiethanol amine (MDEA) in aqueous solutions is presented. Separation was achieved by zwitterionic hydrophilic interaction liquid chromatography (ZIC-HILIC). Injections of aqueous solutions were enabled by on-column focusing with partially filled loop injections. The ZIC-HILIC was coupled with a tandem mass spectrometer (MS/MS) with electrospray ionisation monitoring of positive ions. Linear calibration graphs (0.04-3.0 μg mL-1, n = 9) were obtained with correlation coefficients in the range of >0.96 using N-tripropyl amine (NTPN) as internal standard and >0.99 using NPA as internal standard. The instrumental detection limit was below 44 fmol.

Chromatographic separation of the 10 studied alkanolamines was achieved. The most suitable composition of the focusing liquid was determined to be 1:1 AcCN/AcO, enabling injection volumes up to 3 µL whilst maintaining the chromatographic characteristics. The optimal solvent composition was found to be 100 % water with 0.01 % acid at pH < 4. Sample solution concentrations of 1.0 µg mL-1 could be injected on the column with sustained chromatography.

To maintain stable chromatography the column needed to be regenerated after approximately 500 injections. A minimum of 5 minutes equilibration time between runs was required. The importance of equilibration was also observed after regeneration of the column to obtain chromatographic stability (peak shape and retention times), especially for the compounds eluting close to the front.

Characterisation of the MS fragmentation pattern for the alkanolamines by hydrogen-deuterium exchange indicated a main loss of one or more water molecules. For secondary and tertiary alkanolamines the loss of an alkyl-group and/or alkanol-group was also seen.

The possibility of using the method for determining alkanolamines in metal working fluids and in air samples was demonstrated.

Place, publisher, year, edition, pages
2013. Vol. 3, no 5-6, 298-313 p.
Keyword [en]
Alkanolamine, HILIC, LC-MSMS
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
URN: urn:nbn:se:su:diva-94064DOI: 10.1080/22297928.2013.861166OAI: oai:DiVA.org:su-94064DiVA: diva2:651122
Available from: 2013-09-24 Created: 2013-09-24 Last updated: 2014-06-19Bibliographically approved
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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