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Isocyanates, Amines and Alkanolamines: Sampling, Chromatography and Detection
Stockholm University, Faculty of Science, Department of Analytical Chemistry.
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 [en]
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: urn:nbn:se:su:diva-94067ISBN: 978-91-7447-747-4 (print)OAI: oai:DiVA.org:su-94067DiVA: diva2:651135
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
List of papers
1. Dry Sampling of Gas-Phase Isocyanates and Isocyanate Aerosols from Thermal Degradation of Polyurethane
Open this publication in new window or tab >>Dry Sampling of Gas-Phase Isocyanates and Isocyanate Aerosols from Thermal Degradation of Polyurethane
Show others...
2014 (English)In: Annals of Occupational Hygiene, ISSN 0003-4878, E-ISSN 1475-3162, Vol. 58, no 1, 28-49 p.Article in journal (Refereed) Published
Abstract [en]

The performance of a dry sampler, with an impregnated denuder in series with a glass fibre filter, using di-n-butylamine (DBA) for airborne isocyanates (200ml min−1) is investigated and compared with an impinger flask with a glass fibre filter in series (1 l min−1). An exposure chamber containing 1,6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), and 2,4- and 2,6-toluene diisocyanate (TDI) in the concentration range of 5–205 μg m−3 [0.7–33 p.p.b.; relative humidity (RH) 50%], generated by gas- and liquid-phase permeation, was used for the investigation. The precision for the dry sampling for five series with eight samplers were in the range of 2.0–6.1% with an average of 3.8%. During 120-min sampling (n = 4), no breakthrough was observed when analysing samplers in series. Sixty-four exposed samplers were analysed after storage for 0, 7, 14, and 21 days. No breakdown of isocyanate derivatives was observed. Twenty-eight samplers in groups of eight were collecting isocyanates during 0.5–32h. Virtually linear relationships were obtained with regard to sampling time and collected isocyanates with correlation coefficients in the range of 0.998–0.999 with the intercept close to the origin. Pre- or post-exposure to ambient air did not affect the result. Dry sampling (n = 48) with impinger-filter sampling (n = 48) of thermal decomposition product of polyurethane polymers, at RH 20, 40, 60, and 90%, was compared for 11 isocyanate compounds. The ratio between the different isocyanates collected with dry samplers and impinger-filter samplers was in the range of 0.80–1.14 for RH = 20%, 0.8–1.25 for RH = 40%, 0.76–1.4 for RH = 60%, and 0.72–3.7 for RH = 90%. Taking into account experimental errors, it seems clear that isocyanic acid DBA derivatives are found at higher levels in the dry samples compared with impinger-filter samplers at elevated humidity. The dry sampling using DBA as the reagent enables easy and robust sampling without the need of field extraction.

Keyword
airborne isocyanates, dibutylamine derivatives, dry sampling, liquid chromatography–mass spectrometry, thermal decomposition
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-78817 (URN)10.1093/annhyg/met046 (DOI)000330833300004 ()23960047 (PubMedID)
Note

AuthorCount: 6;

Funders:

Swedish government;  Stockholm University 

Available from: 2012-09-05 Created: 2012-08-13 Last updated: 2017-12-07Bibliographically approved
2. Determination of aromatic amines in aqueous extracts of polyurethane foam using hydrophilic interaction liquid chromatography and mass spectrometry
Open this publication in new window or tab >>Determination of aromatic amines in aqueous extracts of polyurethane foam using hydrophilic interaction liquid chromatography and mass spectrometry
2010 (English)In: Analytica Chimica Acta, ISSN 0003-2670, E-ISSN 1873-4324, Vol. 678, no 1, 117-123 p.Article in journal (Refereed) Published
Abstract [en]

A method is presented for the determination of aromatic amines in aqueous extracts of polyurethane (PUR) foam. The method is based on the extraction of PUR foam using aqueous acetic acid (0.1%, w/v) followed by determination of extracted aromatic amines using hydrophilic interaction liquid chromatography (HILIC) and tandem mass spectrometry (MS/MS) with positive electrospray ionisation. The injections of volumes up to 5 mu L of aqueous solutions were made possible by on-column focusing with partially filled loop injections. The fragmentation patterns for 2,4- and 2,6-toluene diamine (TDA) and 4,4'-methylene dianiline (MDA) were clarified by performing a hydrogen-deuterium exchange study. TDA and MDA were determined using trideuterated 2,4- and 2,6-TDA and dideuterated 4,4'-MDA as internal standards. Linear calibration graphs were obtained over the range 0.025-0.5 mu g mL(-1) with correlation coefficients >0.996 and the instrumental detection limit for each compound was <50 fmol. The stability of the amines was influenced by the matrix, so their concentrations decreased over time. Agreement was observed between the results of analyses of PUR foam extracts by HILIC-MS/MS and results obtained by ethyl chloroformate derivatisation and reversed phase (RP) liquid chromatography-mass spectrometry (LC-MS/MS). TDA was observed to be unstable in extracts of foam but not in pure solutions.

Keyword
Polyurethane (PUR) foam, Hydrogen-deuterium exchange, Liquid chromatography-electrospray tandem mass spectrometry, Hydrophilic interaction liquid chromatography (HILIC), Toluene diamine (TDA), Methylene dianiline (MDA)
National Category
Natural Sciences
Identifiers
urn:nbn:se:su:diva-51747 (URN)10.1016/j.aca.2010.08.020 (DOI)000282850800016 ()
Note

authorCount :4

Available from: 2011-01-12 Created: 2011-01-12 Last updated: 2017-12-11Bibliographically approved
3. A novel sampler for aliphatic amines and a new method for determination using hydrophilic interaction liquid chromatography tandem mass spectrometry
Open this publication in new window or tab >>A novel sampler for aliphatic amines and a new method for determination using hydrophilic interaction liquid chromatography tandem mass spectrometry
(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
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:nbn:se:su:diva-93921 (URN)
Available from: 2013-09-24 Created: 2013-09-19 Last updated: 2014-01-23
4. Analysis of Aqueous Alkanolamines using Hydrophilic Interaction Liquid Chromatography and Mass Spectrometr
Open this publication in new window or tab >>Analysis of Aqueous Alkanolamines using Hydrophilic Interaction Liquid Chromatography and Mass Spectrometr
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.

Keyword
Alkanolamine, HILIC, LC-MSMS
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-94064 (URN)10.1080/22297928.2013.861166 (DOI)
Available from: 2013-09-24 Created: 2013-09-24 Last updated: 2014-06-19Bibliographically approved
5. A novel sampler for alkanolamines and a new method for determination using hydrophilic interaction liquid chromatography tandem mass spectrometry
Open this publication in new window or tab >>A novel sampler for alkanolamines and a new method for determination using hydrophilic interaction liquid chromatography tandem mass spectrometry
2014 (English)In: Annals of Occupational Hygiene, ISSN 0003-4878, E-ISSN 1475-3162Article in journal (Refereed) Accepted
Abstract [en]

A novel sampler for determination of airborne alkanolamines 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 quantifications with linear correlation coefficients > 0.992,  instrumental precision (n = 16) of < 6 %  and detection limits of 5.1 – 48 pg for ethanol amine (EA), n-propanol amine (NPA), isopropanol amine (IPA), dimethylethanol amine (DMEA), diethanol amine (DEA), diethylethanol amine (DEEA), methyldiethanol amine (MDEA), diisopropanol amine (DIPA) and triethanolamine (TEA).

The performance of the sampler was investigated by sampling a standard atmosphere of EA, IPA, DMEA, DEEA and MDEA (0.03-6.1 mg m-3) in an exposure chamber (0.3 m3). The air concentrations of the amines were generated by liquid phase membrane permeation.

The extraction recovery for spiked samplers (10 μg) was in the range 93-106 %. The precision when sampling three series of ten samplers each was in the range 2.1-4.8 %. No breakthrough was observed from the sampler when sampling during 60 min using four sets of two samplers in sequence at a flow rate of 0.2 L min-1. A minor breakthrough was observed for DEEA and DMEA at 0.8 L min-1 and the collection efficiencies were > 99.4 %. The distribution of the alkanolamines in the sampler was studied by dissection of the denuders (into eight parts) for two different flow rates (0.2 and 1.1 L min-1). The first parts of the denuder collected the highest amount of alkanolamines, which then declined throughout the remaining parts. It was observed that the denuder was too short to collect all the gas phase alkanolamines 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 sampling. No degradation of the alkanolamines on the sampler was observed when exposed samplers were stored for up to 45 days. When sampling DMEA and DEEA, over a period of 0.5 - 8 h (n = 6), linear relationships were obtained with correlation coefficients > 0.998. Using sampling flow rates of 0.05 - 0.8 L min−1, linear relationships were obtained with correlation coefficients > 0.974. 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
Alkanolamines, Hydrophilic Interaction Liquid Chromatography, HILIC, dry sampling, liquid chromatography–mass spectrometry, Denuder, filter, sampler
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-93918 (URN)
Available from: 2013-09-24 Created: 2013-09-19 Last updated: 2017-11-09Bibliographically approved

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