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New methods for determination of airborne pollutants: Focus on tetrabromobisphenol A, organophosphate triesters and polycyclic aromatic hydrocarbons
Stockholm University, Faculty of Science, Department of Analytical Chemistry.
2009 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The work presented in this thesis concerns the development and evaluation of new methods of sampling and analysis of organic pollutants in the indoor and outdoor environment.

In Paper I, the development of a new method was reported for the determination of the brominated flame retardant tetrabromobisphenol A (TBBPA) in air using sampling with glass fiber filter and polyurethane foam (PUF), ultrasonic solvent extraction and liquid chromatography coupled to electrospray ionisation mass spectrometry (LC-ESI/MS). The MS fragmentation mechanism of TBBPA was thoroughly investigated and different acquisition modes were evaluated to achieve the most sensitive and selective detection.

In Papers II and III, the potential use of Empore SPE membranes was evaluated for air sampling of volatile, semi-volatile and particle-associated organic compounds. Breakthrough studies conducted for 24h at air flows of 10- 20 L/min showed that the SPE membranes efficiently retains volatile and semi-volatile organophosphate esters and particles >10 nm. Effort was invested in the development of fast and environmental friendly methods, with low cost, for sample clean up and analysis.

In Paper II, the sample preparation technique was dynamic solvent extraction with methanol coupled to LC-ESI/MS. The total run time per sample, including both extraction and separation, was less than 34 min, consuming only 1.6mL methanol. In Paper III, efficiency of selective extraction of polycyclic aromatic hydrocarbons from particulate matter sampled with Empore SPE membranes, using dynamic subcritical water extraction (DSWE) was investigated. Acceptable recoveries of the investigated compounds from reference material (SRM 1649a) were achieved. In Paper IV, the application of dynamic solid phase micro-extraction (SPME) air sampling was evaluated using, gas chromatography/positive ion chemical ionisation (GC/PICI) and tandem-MS detection for the determination of organophosphate esters in work environment.

Place, publisher, year, edition, pages
Stockholm: Department of Analytical Chemistry, Stockholm University , 2009. , 80 p.
Keyword [en]
Air sampling, sampling methods, indoor air, SPE, SPME, extraction, dynamic extraction, online coupling, SWE, subcritical water extraction, GC/MS, LC/MS, organophosphate triesters, PAH, tetrabromobisphenol A
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
URN: urn:nbn:se:su:diva-26700ISBN: 978-91-7155-843-5 (print)OAI: oai:DiVA.org:su-26700DiVA: diva2:211116
Public defence
2009-05-14, Magnélisalen, Kemiska Övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 13:00 (Swedish)
Opponent
Supervisors
Available from: 2009-04-23 Created: 2009-04-07 Last updated: 2010-12-14Bibliographically approved
List of papers
1. Feasibility of analyzing fine particulate matter in air using solid-phase extraction membranes and dynamic subcritical water extraction
Open this publication in new window or tab >>Feasibility of analyzing fine particulate matter in air using solid-phase extraction membranes and dynamic subcritical water extraction
2008 (English)In: Analytical chemistry, ISSN 1520-6882, Vol. 80, no 9, 3159-67 p.Article in journal (Refereed) Published
Abstract [en]

We have evaluated the feasibility of using Empore solid-phase extraction (SPE) membranes as an alternative to conventional techniques for sampling fine airborne particulate matter (PM), including nanoparticles, utilizing a scanning mobility particle sizer (SMPS) and a condensation particle counter to evaluate their efficiency for trapping fine particles in the 10-800 nm size range. The results demonstrate that the membranes can efficiently trap these particles and can then be conveniently packed into an extraction cell and extracted under matrix solid-phase dispersion (MSPD) conditions. The potential utility of sampling PM using Empore membranes followed by dynamic subcritical water extraction (DSWE) for fast, efficient, class-selective extraction of polycyclic aromatic hydrocarbons (PAHs) associated with the particles, prior to changing the solvent and analysis by GC/MS, was then explored. The performance of the method was tested using National Institute of Standards and Technology (NIST)-certified "urban dust" reference material (SRM 1649a) and real samples collected at a site in central Rome with heavy road traffic. The method appears to provide comparable extraction efficiency to that of conventional techniques and with using GC/MS, detection limits ranged in the few picograms per cubic meter level. Sampling PM by Empore membranes may reduce the risks of losses of semivolatile compounds, while allowing relatively high sampling flow rates and safe sample storage. Moreover, the combination of MSPD with DSWE permits specific fractions of the PM components to be eluted, thereby generating clean extracts and reducing both analysis time and sample manipulation.

National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-26596 (URN)10.1021/ac7021458 (DOI)18393539 (PubMedID)
Available from: 2009-04-07 Created: 2009-04-02 Last updated: 2009-04-08Bibliographically approved
2. Determination of the flame retardant tetrabromobisphenol A in air samples by liquid chromatography-mass spectrometry.
Open this publication in new window or tab >>Determination of the flame retardant tetrabromobisphenol A in air samples by liquid chromatography-mass spectrometry.
2006 (English)In: Journal of Chromatography A, ISSN 0021-9673, E-ISSN 1873-3778, Vol. 1104, no 1-2, 106-12 p.Article in journal (Refereed) Published
Abstract [en]

An original method based on LC-MS for determination of the flame retardant tetrabromobisphenol A (TBBPA) in air is presented, as an alternative to the traditionally used GC-MS. The soft ionization in LC-MS makes it possible to monitor the intact molecule and to use 13C-labelled TBBPA as an internal surrogate standard, two features that improve both accuracy and precision of the analyses. Comparison of different acquisition modes in electrospray ionization showed that the lowest detections limit, 3.1 pg TBBPA injected, was obtained in SIM monitoring the molecular ions 542.7/544.7. A fragmentation pathway of TBBPA in LC-ESI-MS is suggested. The only sample clean-up steps required are solvent reduction and filtration of the sample extract. Recoveries were 93% at a 30 ng level and 75% at 3 ng. The new method was tested by analyses of air samples collected at a recycling plant for electronic equipment. The amount of TBBPA found was 13.8 ng/m3 with an RSD of 5.9%. Furthermore, it was found that TBBPA in a standard solution could be partially debrominated, if not carefully protected from light during storage.

National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-26592 (URN)10.1016/j.chroma.2005.11.067 (DOI)16337636 (PubMedID)
Available from: 2009-04-07 Created: 2009-04-02 Last updated: 2017-12-13Bibliographically approved
3. Dynamic non-equilibrium SPME combined with GC, PICI, and ion trap MS for determination of organophosphate esters in air
Open this publication in new window or tab >>Dynamic non-equilibrium SPME combined with GC, PICI, and ion trap MS for determination of organophosphate esters in air
2010 (English)In: Analytical and Bioanalytical Chemistry, ISSN 1618-2642, E-ISSN 1618-2650, Vol. 396, no 2, 839-844 p.Article in journal (Refereed) Published
Abstract [en]

Methodology for time-weighted average (TWA) air measurements of semivolatile organophosphate triesters, widely used flame-retardants and plasticizers, and common indoor pollutants is presented. Dynamic non-equilibrium solid-phase microextraction (SPME) for air sampling, in combination with GC/PICI and ion trap tandem MS, yields a fast, almost solvent-free method with low detection limits. Methanol was used as reagent gas for PICI, yielding stable protonated molecules and few fragments. A field sampler, in which a pumped airflow over three polydimethylsiloxane (PDMS) 100-μm fibers in series was applied, was constructed, evaluated, and used for the measurements. The method LODs were in the range 2–26 ng m−3 for a sampling period of 2 h. The uptake on the SPME fibers was shown to be about five times faster for triphenyl phosphate compared to the other investigated organophosphate esters, most likely due to more lipophilic properties of the aromatic compound. The boundary layer for triphenyl phosphate when using a 100-µm PDMS sorbent was determined to 0.08 mm at a linear air velocity of 34 cm s−1. Five different organophosphate triesters were detected in air from a laboratory and a lecture hall, at concentrations ranging from 7 ng m−3 up to 2.8 μg m−3.

Place, publisher, year, edition, pages
Berlin: Springer, 2010
Keyword
Organophosphate triesters, SPME, Non-equilibrium, Dynamic air sampling, PICI, GC/MS/MS
National Category
Natural Sciences
Identifiers
urn:nbn:se:su:diva-34673 (URN)10.1007/s00216-009-3221-y (DOI)
Available from: 2010-01-11 Created: 2010-01-11 Last updated: 2017-12-12Bibliographically approved
4. Air sampling with Empore solid phase extraction membranes and online single-channel desorption/liquid chromatography/mass spectrometry analysis: Determination of volatile and semi-volatile organophosphate esters
Open this publication in new window or tab >>Air sampling with Empore solid phase extraction membranes and online single-channel desorption/liquid chromatography/mass spectrometry analysis: Determination of volatile and semi-volatile organophosphate esters
2006 (English)In: Journal of Chromatography A, ISSN 0021-9673, E-ISSN 1873-3778, Vol. 1129, no 1, 1-8 p.Article in journal (Refereed) Published
Abstract [en]

A method for determining organophosphate esters in air samples using C8 Empore solid phase extraction (SPE) membranes has been developed. After the sampling the analytes trapped in the membrane are completely desorbed with methanol, using an extraction cell connected online to the organic modifier channel of a HPLC gradient pump. The addition of water to the mobile phase prior to analytical chromatography ensures that the analytes are refocused and efficiently separated. Sampling with Empore SPE membranes enables the collection of analytes in both the vapour phase and particulate matter. During the air sampling procedure no losses were observed after 24 h of sampling, yielding a total volume of 14.4 m3, even for the most volatile compound used in this investigation (trimethylphosphate). Complete desorption was observed for all the organophosphate esters and recoveries were greater than 95%, with a relative standard deviation of less than 8%. The limits of detection ranged between 0.4 and 19 pg/m3. The effect of particulate matter on the extraction efficiency was investigated in detail by spiking the membranes with reference standard material. It was also found that the SPE membranes could be stored for at least 5 days at room temperature without any evidence of loss. The efficacy of the method was verified using real samples from different common indoor environments. Interestingly, significant quantities of several phosphate esters were found in a NIST standard reference material (urban dust, SRM 1649a).

Keyword
Air sampling; Air analysis; Online; Single-channel desorption; Dynamic solvent extraction; Extraction methods; LC-MS; Volatile; Semi-volatile; Organophosphate esters; Empore disk; Solid phase extraction; SPE; Membranes; Particulate matter; Urban dust; Environmental analysis; Organophosphorus compounds; Phosphate
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-26595 (URN)10.1016/j.chroma.2006.05.086 (DOI)16934277 (PubMedID)
Available from: 2009-04-07 Created: 2009-04-02 Last updated: 2017-12-13Bibliographically approved

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