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Dry Sampling of Gas-Phase Isocyanates and Isocyanate Aerosols from Thermal Degradation of Polyurethane
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.
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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.

Place, publisher, year, edition, pages
2014. Vol. 58, no 1, 28-49 p.
Keyword [en]
airborne isocyanates, dibutylamine derivatives, dry sampling, liquid chromatography–mass spectrometry, thermal decomposition
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
URN: urn:nbn:se:su:diva-78817DOI: 10.1093/annhyg/met046ISI: 000330833300004PubMedID: 23960047OAI: oai:DiVA.org:su-78817DiVA: diva2:549965
Note

AuthorCount: 6;

Funders:

Swedish government;  Stockholm University 

Available from: 2012-09-05 Created: 2012-08-13 Last updated: 2017-12-07Bibliographically 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
2. 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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