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Determination of Gas Phase Isocyanates Using Proton Transfer Reaction 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.
2011 (English)In: Analytical Chemistry Letters, ISSN 2229-7928, Vol. 1, no 4, 261-271 p.Article in journal (Refereed) Published
Abstract [en]

We report the development of proton transfer reaction-mass spectrometry (PTR-MS) methodology for on-line monitoring, using a direct reading instrument, of several typical gas phase isocyanates, including isocyanic acid (ICA), ethyl isocyanate (EIC), phenyl isocyanate (PhI), hexamethylene diisocyanate (HDI) and toluene diisocyanate (TDI). In the study, ICA and MIC were generated by thermal degradation of urea and 1,3-dimethylurea, respectively, while the other isocyanates were generated by liquid and gas permeation techniques. Comparative, reference measurements were made by sampling isocyanate atmosphere using impinger flasks containing the reagent di-n-butyl amine (DBA) then determining the resulting DBA derivatives by liquid chromatography (LC)-MS/MS. Reproducible measurements were obtained, with a <10 % drift in PTR-MS responses during a 12 month period. Further, there were linear correlations (R2>0.99) between the data acquired by the PTR-MS technique and air sampling followed by LC-MS/MS for all tested isocyanates in the concentration range 2-100 ppb, with a PTR-MS detection limits in the low ppb range. For all isocyanates except EIC, BIC, HDI and IPDI, the protonated molecular ions were the most abundant ions in the PTR mass spectra. Overall, the results show that the developed method enables sensitive, time-resolved measurements of airborne isocyanates to be acquired over several weeks.

Place, publisher, year, edition, pages
2011. Vol. 1, no 4, 261-271 p.
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
URN: urn:nbn:se:su:diva-79556DOI: 10.1080/22297928.2011.10648228OAI: oai:DiVA.org:su-79556DiVA: diva2:549969
Available from: 2012-09-05 Created: 2012-09-05 Last updated: 2013-10-15Bibliographically approved
In thesis
1. Isocyanates - methodology for gas and particle generation, sampling and detection
Open this publication in new window or tab >>Isocyanates - methodology for gas and particle generation, sampling and detection
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Isocyanates are mainly used in the industry for the production of polyurethane (PUR) plastics. Workers are at risk of being exposed during the manufacturing of PUR. During thermal degradation of PUR, isocyanates are released and workers involved in hot work such as fire-fighting, welding etc. may also be exposed.

Isocyanates are known to cause allergic diseases and are the most common cause of occupational asthma. Some of the isocyanates used are suspected human carcinogens. Exposure among workers occurs frequently.

Isocyanates are reactive unstable compounds that need to be converted to stabile derivatives immediately during sampling to avoid underestimation of the exposure. Di-n-ButylAmine (DBA) was used as derivatising reagent to form stable urea derivatives. The DBA derivatives were analysed using LC-MS/MS.

In this thesis a novel technology for the direct monitoring of isocyanates using a Proton Transfer Reaction Mass Spectrometry (PTR-MS) is presented. Advancement of technology for the generation of isocyanates in an environmental chamber, dry sampling, particle-size fractionated sampling and the testing of respirator filter cartridges are described.

The dry sampler was demonstrated to be robust and enabled sampling up to 32 h. Precise sampling without the need of field extraction was made possible.

The particle-size fractionated sampling efficiently separated gas-phase and respirable particle-borne isocyanates (< 4µm in diameter).

Two personal protective respirator filter cartridges were studied. No trend of impaired performance for mono-isocyanates throughout 48-h exposure tests was found.

The distribution patterns, in a steady-state tube-furnace oven, between gas phase and different particle-phase fractions of isocyanates produced in fires were investigated. The substantial degradation of a PVC-carpet containing PUR and a wood board with a MDI based binder resulted mainly in the formation of high levels of monoisocyanates.

Place, publisher, year, edition, pages
Stockholm: Department of Analytical Chemistry, Stockholm University, 2012. 107 p.
Keyword
Isocyanate, PUR, Dry sampler, PTR-MS, Transfer line, PPE, Environmental Chamber, Respirable Particles, Denuder Impactor, Aerosol, Particles, Impinger, air sampling, LC-MS, di-n-butylamine, DBA, ICA, MIC, HDI, TDI, IPDI, MDI, Occupational Exposure, Exposure, Occupational Health
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-79501 (URN)978-91-7447-556-2 (ISBN)
Public defence
2012-10-05, Vita salen, Hässleholm Kulturhus, Vattugatan 18/Järnvägsgatan 23, Hässleholm, Hässleholm, 10:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 1: Submitted. Paper 2: Submitted. Paper 5: Accepted.

Available from: 2012-09-13 Created: 2012-09-04 Last updated: 2014-03-17Bibliographically approved

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