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Solid-phase Microextraction and Detection of Organophosphate Triesters in Indoor air
Stockholm University, Faculty of Science, Department of Analytical Chemistry.
2004 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

In the work underlying this thesis solid-phase microextraction (SPME) was evaluated as a passive sampling technique for organophosphate triesters in indoor air. These compounds are used on a large scale as flame-retarding and plastizicing additives in a variety of materials and products, and have proven to be common pollutants in indoor air. The main objective of this work was to develop an accurate method for measuring the volatile fraction. Such a method can be used in combination with active sampling to obtain information regarding the vapour/particulate distribution in different indoor environments. SPME was investigated under both equilibrium and non-equilibrium conditions and parameters associated with these different conditions were estimated.

In Paper I, time-weighted average (TWA) SPME under dynamic conditions was investigated in order to obtain a fast air sampling method for organophosphate triesters. Among the investigated SPME coatings, the absorptive PDMS polymer had the highest affinity for the organophosphate triesters and was consequently used in all further work. Since the sampling rate is dependent on the agitation conditions, the linear airflow rates had to be carefully considered. Sampling periods as short as 1 hour were shown to be sufficient for measurements in the ng-μg m-3 range when using a PDMS 100-μm fibre and a linear flow rate above 7 cm s-1 over the fibre.

SPME under equilibrium conditions is rather time-consuming, even under dynamic conditions, for slowly partitioning compounds such as organophosphate triesters. Nevertheless, this method has some significant advantages. For instance, the limit of detection is much lower compared to 1 h TWA sampling. Furthermore, the sampling time can be ignored as long as equilibrium has been attained. In Paper II, SPME under equilibrium conditions was investigated and evaluated for organophosphate triester vapours. Since temperature and humidity are closely associated with the distribution constant a simple study of the effect of these parameters was performed. The obtained distribution constants were used to determine the air levels in a common indoor environment. SPME and parallel active sampling on filters yielded similar results, indicating that the detected compounds were almost entirely associated with the vapour phase

To apply dynamic SPME method in the field a sampler device, which enables controlled linear airflow rates to be applied, was constructed and evaluated (Paper III). This device was developed for application of SPME and active sampling in parallel.

A GC/PICI-MS/MS method was developed and used in combination with active sampling of organophosphate triesters in indoor air (Paper IV). The combination of MS/MS and the soft ionization achieved with methanol as reagent gas yielded high selectivity and detection limits comparable to those provided by GC with nitrogen-phosphorus detection (NPD). The method limit of detection, when sampling 1.5 m3 of air, was in the range 0.1-1.4 ng m-3. In Paper V, the developed MS method was used in combination with SPME for indoor air measurements.

The levels detected in the investigated indoor environments range from a few ng to μg m-3. Tris(2-chloropropyl) phosphate was detected at a concentration as high as 7 μg m-3 in a newly rebuilt lecture room.

Place, publisher, year, edition, pages
Stockholm: Institutionen för analytisk kemi , 2004. , 62 p.
Keyword [en]
SPME, Organophosphate triesters, flame-retardant, indoor air
National Category
Analytical Chemistry
Identifiers
URN: urn:nbn:se:su:diva-244ISBN: 91-7265-954-8 (print)OAI: oai:DiVA.org:su-244DiVA: diva2:191431
Public defence
2004-10-06, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 13:00
Opponent
Supervisors
Available from: 2004-09-15 Created: 2004-09-15Bibliographically approved
List of papers
1. Air sampling of organophosphate triesters using SPME under non-equilibrium conditions
Open this publication in new window or tab >>Air sampling of organophosphate triesters using SPME under non-equilibrium conditions
2004 In: Analytical and Bioanalytical Chemistry, ISSN 1618-2642, Vol. 378, no 7, 1847-1853 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-23331 (URN)
Note
Part of urn:nbn:se:su:diva-244Available from: 2004-09-15 Created: 2004-09-15Bibliographically approved
2. Evaluation of solid-phase microextraction with PDMS for air sampling of gaseous organophosphate flame-retardants and plasticizers
Open this publication in new window or tab >>Evaluation of solid-phase microextraction with PDMS for air sampling of gaseous organophosphate flame-retardants and plasticizers
2004 (English)In: Analytical and Bioanalytical Chemistry, ISSN 1618-2642, E-ISSN 1618-2650, Vol. 380, no 2, 319-324 p.Article in journal (Refereed) Submitted
Abstract [en]

As an inexpensive, simple, and low-solvent consuming extraction technique, the suitability of solid-phase microextraction (SPME) with polydimethylsiloxane (PDMS) sorbent was investigated as a quantitative method for sampling gaseous organophosphate triesters in air. These compounds have become ubiquitous in indoor air, because of their widespread use as additive flame retardants/plasticizers in various indoor materials. Results obtained by sampling these compounds at controlled air concentrations using SPME and active sampling on glass fibre filters were compared to evaluate the method. A constant linear airflow of 10 cm s–1 over the fibres was applied to increase the extraction rate. For extraction of triethyl phosphate with a 100-m PDMS fibre, equilibrium was achieved after 8 h. The limit of detection was determined to be less than 10 pg m–3. The PDMS–air partition coefficients, Kfs, for the individual organophosphate triesters were determined to be in the range 5–60×106 at room temperature (22–23°C). Air measurements were performed utilising the determined coefficients for quantification. In samples taken from a lecture room four different airborne organophosphate esters were identified, the most abundant of which was tris(chloropropyl) phosphate, at the comparatively high level of 1.1 g m–3. The results from SPME and active sampling had comparable repeatability (RSD less than 17%), and the determined concentrations were also similar. The results suggest that the investigated compounds were almost entirely associated with the gaseous phase at the time and place sampled.

Place, publisher, year, edition, pages
Springer, 2004
Keyword
Organophosphate triesters * Flame retardants * Plasticizers * Air sampling * SPME * PDMS
National Category
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-23332 (URN)10.1007/s00216-004-2760-5 (DOI)
Note
Part of urn:nbn:se:su:diva-244Available from: 2004-09-15 Created: 2004-09-15 Last updated: 2017-12-13Bibliographically approved
3. Dynamic field sampling of airborne organophosphate triesters using solid-phase microextraction under equilibrium and non-equilibrium conditions
Open this publication in new window or tab >>Dynamic field sampling of airborne organophosphate triesters using solid-phase microextraction under equilibrium and non-equilibrium conditions
2005 (English)In: The Analyst, ISSN 0003-2654, E-ISSN 1364-5528, Vol. 30, 94-98 p.Article in journal (Refereed) Published
Abstract [en]

 

A simple setup for dynamic air sampling using a solid-phase microextraction (SPME) device

designed for use in the field was evaluated for organophosphate triester vapour under both

equilibrium and non-equilibrium conditions. The effects of varying the applied airflows in the

sampling device were evaluated in order to optimise the system with respect to the Reynolds

number and magnitude of the boundary layer that developed near the surface. Further, the

storage stability of the analytes was studied for both capped and uncapped 100-

 

 

m

m PDMS fibres.

Organophosphate triesters are utilized on large scales as flame-retardants and/or plasticizers, for

instance in upholstered furniture. In indoor working environments these compounds have become

common components in the surrounding air. Measurements were performed in a recently

furnished working environment and the concentration of tris(2-choropropyl) phosphate was

found to be 7

 

 

mg m23

.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2005
National Category
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-23333 (URN)10.1039/B410597D (DOI)
Note
Part of urn:nbn:se:su:diva-244Available from: 2004-09-15 Created: 2004-09-15 Last updated: 2017-12-13Bibliographically approved
4. Selective determination of organophosphate flame-retardants and plasticizers in indoor air by gas chromatography, positive-ion chemical ionization and collision-induced dissosiation mass spectrometry
Open this publication in new window or tab >>Selective determination of organophosphate flame-retardants and plasticizers in indoor air by gas chromatography, positive-ion chemical ionization and collision-induced dissosiation mass spectrometry
2004 (English)In: Rapid Communications in Mass Spectrometry, ISSN 0951-4198, E-ISSN 1097-0231, Vol. 18, no 24, 3079-3083 p.Article in journal (Refereed) Published
Abstract [en]

Gas chromatography/ion trap mass spectrometry with in-source ionization and dissociation was used in positive-ion chemical ionization (PICI) mode for the determination of organophosphate triesters in indoor air. These compounds are widely used as additive flame retardants and plasticizers in different types of materials and have become ubiquitous pollutants in indoor environments. When using collision-induced dissociation in PICI mode the fragmentation of the organophosphate triesters can be performed in a more controllable way than in electron ionization (EI) mode. The developed selected-reaction monitoring method provided high selectivity for the investigated compounds. For 8-h air measurements (corresponding to 1.5 m3 of sampled air) the limit of detection of the method was determined to be in the range 0.1–1.4 ng m−3, which is comparable with nitrogen-phosphorus detection and about 50-fold lower than when using EI in selected-ion monitoring mode. The presented method was applied to samples from three common indoor environments, in which a number of organophosphate triesters were identified and quantified. The dominating compound was found to be tris(2-chloropropyl) phosphate, which occurred at levels up to 0.8 μg m−3.

Identifiers
urn:nbn:se:su:diva-23334 (URN)10.1002/rcm.1721 (DOI)
Note
Part of urn:nbn:se:su:diva-244Available from: 2004-09-15 Created: 2004-09-15 Last updated: 2017-12-13Bibliographically approved
5. Application of non-equilibrium SPME combined with GC, PICI and ion trap tandem MS for determination of airborne organophosphate flame-retardants and plasticizers in work environments
Open this publication in new window or tab >>Application of non-equilibrium SPME combined with GC, PICI and ion trap tandem MS for determination of airborne organophosphate flame-retardants and plasticizers in work environments
Manuscript (Other academic)
Identifiers
urn:nbn:se:su:diva-23335 (URN)
Note
Part of urn:nbn:se:su:diva-244Available from: 2004-09-15 Created: 2004-09-15 Last updated: 2010-01-13Bibliographically approved

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