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Determination of Polycyclic Aromatic Hydrocarbons in Various Environmental Matrices: Emphasis on extraction method development
Stockholm University, Faculty of Science, Department of Analytical Chemistry.
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Very recently, air pollution was declared the world’s single largest environmental health risk by the World Health Organization. The goal of this thesis is to contribute to a better assessment of air pollution through the development of novel and exhaustive extraction methods for the analysis of polycyclic aromatic hydrocarbons (PAHs), which are mutagenic and carcinogenic air pollutants.

The methods were developed and validated for the extraction of PAHs in both the semi-volatile fraction and particulate matter with application to samples derived from major sources of PAHs (diesel exhaust, coal fly ash and wood smoke samples). Pressurized liquid extraction was used because it allows a high sample throughput with reduced solvent requirements and analysis time compared to other traditionally used techniques, such as Soxhlet extraction.

The results presented herein show that the extraction conditions used when analyzing PAHs need to be evaluated to avoid underestimating their concentrations. This is especially true for the human carcinogen benzo[a]pyrene, which is often used as an indicator in the cancer risk assessments of PAHs, and the dibenzopyrene isomers due to their potentially high carcinogenicities.

Place, publisher, year, edition, pages
Stockholm: Department of Analytical Chemistry, Stockholm University , 2014. , p. 56
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
URN: urn:nbn:se:su:diva-107175ISBN: 978-91-7447-964-5 (print)OAI: oai:DiVA.org:su-107175DiVA, id: diva2:743722
Public defence
2014-10-09, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 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At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Accepted. Paper 4: Manuscript.

Available from: 2014-09-18 Created: 2014-09-04 Last updated: 2018-09-13Bibliographically approved
List of papers
1. Improved efficiency of extraction of polycyclic aromatic hydrocarbons (PAHs) from the National Institute of Standards and Technology (NIST) Standard Reference Material Diesel Particulate Matter (SRM 2975) using accelerated solvent extraction
Open this publication in new window or tab >>Improved efficiency of extraction of polycyclic aromatic hydrocarbons (PAHs) from the National Institute of Standards and Technology (NIST) Standard Reference Material Diesel Particulate Matter (SRM 2975) using accelerated solvent extraction
2011 (English)In: Analytical and Bioanalytical Chemistry, ISSN 1618-2642, E-ISSN 1618-2650, Vol. 401, no 10, p. 3305-3315Article in journal (Refereed) Published
Abstract [en]

The efficiency of extraction of polycyclic aromatic hydrocarbons (PAHs) with molecular masses of 252, 276, 278, 300, and 302 Da from standard reference material diesel particulate matter (SRM 2975) has been investigated using accelerated solvent extraction (ASE) with dichloromethane, toluene, methanol, and mixtures of toluene and methanol. Extraction of SRM 2975 using toluene/methanol (9:1, v/v) at maximum instrumental settings (200 A degrees C, 20.7 MPa, and five extraction cycles) with 30-min extraction times resulted in the following elevations of the measured concentration when compared with the certified and reference concentrations reported by the National Institute of Standards and Technology (NIST): benzo[b]fluoranthene, 46%; benzo[k]fluoranthene, 137%; benzo[e]pyrene, 103%; benzo[a]pyrene, 1,570%; perylene, 37%; indeno[1,2,3-cd]pyrene, 41%; benzo[ghi]perylene, 163%; and coronene, 361%. The concentrations of the following PAHs were comparable to the reference values assigned by NIST: indeno[1,2,3-cd]fluoranthene, dibenz[a,h]anthracene, and picene. The measured concentration of dibenzo[a,e]-pyrene was lower than the information value reported by the NIST. The measured concentrations of other highly carcinogenic PAHs (dibenzo[a,l]pyrene, dibenzo[a,i]pyrene, and dibenzo[a,h]pyrene) in SRM 2975 are also reported. Comparison of measurements using the optimized ASE method and using similar conditions to those applied by the NIST for the assignment of PAH concentrations in SRM 2975 indicated that the higher values obtained in the present study were associated with more complete extraction of PAHs from the diesel particulate material. Re-extraction of the particulate samples demonstrated that the deuterated internal standards were more readily recovered than the native PAHs, which may explain the lower values reported by the NIST. The analytical results obtained in the study demonstrated that the efficient extraction of PAHs from SRM 2975 is a critical requirement for the accurate determination of PAHs with high molecular masses in this standard reference material and that the optimization of extraction conditions is essential to avoid underestimation of the PAH concentrations. The requirement is especially relevant to the human carcinogen benzo[a]pyrene, which is commonly used as an indicator of the carcinogenic risk presented by PAH mixtures.

Keywords
Accelerated solvent extraction, ASE, Diesel particulate matter, SRM 2975, PAH, Benzo[a]pyrene, Dibenzo[a, l]pyrene, Dibenzo[a, e]pyrene, Dibenzo[a, i]pyrene, Dibenzo[a, h]pyrene
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-65506 (URN)10.1007/s00216-011-5446-9 (DOI)000297159900026 ()
Available from: 2011-12-12 Created: 2011-12-12 Last updated: 2017-12-08Bibliographically approved
2. Determination of benzo(a)pyrene and dibenzopyrenes in a Chinese coal fly ash Certified Reference Material
Open this publication in new window or tab >>Determination of benzo(a)pyrene and dibenzopyrenes in a Chinese coal fly ash Certified Reference Material
2012 (English)In: Science of the Total Environment, ISSN 0048-9697, E-ISSN 1879-1026, Vol. 432, p. 97-102Article in journal (Other academic) Published
Abstract [en]

Air pollution from coal combustion is of great concern in China because coal is the country's principal source of energy and it has been estimated that coal combustion is one of the main sources of polycyclic aromatic hydrocarbon (PAH) emissions in the nation. This study reports the concentrations of 15 PAHs including benzo[a]pyrene, dibenzo[a,l]pyrene, dibenzo[a,e]pyrene, dibenzo[a,i]pyrene and dibenzo[a,h]pyrene in a coal fly ash certified reference material (CRM) from China. To the best of our knowledge, dibenzo[a,l]pyrene, dibenzo[a,i]pyrene and dibenzo[a,h]pyrene concentrations in coal fly ash particles have not previously been reported. Benzo[a]pyrene is the only one of the studied hydrocarbons whose concentration in the coal fly ash CRM had previously been certified. The concentration of this species measured in this present work was twice the certified value. This is probably because of the exhaustive accelerated solvent extraction method employed. Consecutive extractions indicated an extraction recovery in excess of 95% for benzo[a]pyrene. For the other determined PAHs, repeat extractions indicated recoveries above 90%.

Keywords
PAH, Polycyclic aromatic hydrocarbons, Benzo[a]pyrene, Dibenzopyrenes, Dibenzo[a, l]pyrene, Coal fly ash
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-67531 (URN)10.1016/j.scitotenv.2012.05.081 (DOI)000308270700011 ()
Available from: 2011-12-28 Created: 2011-12-28 Last updated: 2017-12-08Bibliographically approved
3. Pressurized liquid extraction as an alternative to the Soxhlet extraction procedure stated in the US EPA method TO-13A for the recovery of polycyclic aromatic hydrocarbons adsorbed on polyurethane foam plugs
Open this publication in new window or tab >>Pressurized liquid extraction as an alternative to the Soxhlet extraction procedure stated in the US EPA method TO-13A for the recovery of polycyclic aromatic hydrocarbons adsorbed on polyurethane foam plugs
2014 (English)In: Analytical Methods, ISSN 1759-9660, E-ISSN 1759-9679, Vol. 6, no 20, p. 8420-8425Article in journal (Refereed) Published
Abstract [en]

The aim of the present study was to develop a pressurized liquid extraction (PLE) method as an alternative to the relatively time consuming Soxhlet extraction procedure described in the United States Environmental Protection Agency (US EPA) method TO-13A for the extraction of PAHs adsorbed onto polyurethane foam plugs (PUFs). For this purpose PUF air samples were collected and split into two parts: one part extracted using PLE and the other one using Soxhlet extraction. Comparable PAH concentrations were obtained upon analysis of the extracts showing that the PLE method developed in this work is a more convenient choice than the commonly used Soxhlet extraction technique proposed by US EPA for the determination of PAHs in air samples. In fact, the developed PLE method required shorter assay times (minutes versus hours), less solvent consumption and simpler operational methods. The exhaustiveness of the developed PLE method was evaluated using repeat static extraction cycles, demonstrating an extraction efficiency for the PAHs of greater than 99%. The PLE method was then applied to diesel exhaust and wood smoke PUF samples showing an extraction efficiency for the PAHs of greater than 93% and 96%, respectively. Furthermore, a PLE method for PUF cleaning was developed as well and employed as an alternative to Soxhlet extraction. The PLE methods developed for cleaning and extracting PUFs presented in this work are suitable to be used in mutagenicity studies using the Ames Salmonella assay as no mutagenicity was found in the PLE generated blanks

National Category
Analytical Chemistry Biological Sciences
Identifiers
urn:nbn:se:su:diva-107173 (URN)10.1039/c4ay01430h (DOI)000342989400045 ()
Available from: 2014-09-04 Created: 2014-09-04 Last updated: 2017-12-05Bibliographically approved
4. Determination of semi-volatile and particle-associated polycyclic aromatic hydrocarbons in Stockholm air with emphasis on the highly carcinogenic dibenzopyrene isomers
Open this publication in new window or tab >>Determination of semi-volatile and particle-associated polycyclic aromatic hydrocarbons in Stockholm air with emphasis on the highly carcinogenic dibenzopyrene isomers
Show others...
2016 (English)In: Atmospheric Environment, ISSN 1352-2310, E-ISSN 1873-2844, Vol. 140, p. 370-380Article in journal (Refereed) Published
Abstract [en]

The concentrations of polycyclic aromatic hydrocarbons (PAHs) have been determined in the gaseous phase and in various particulate matter (PM) size fractions at different locations in and outside of Stockholm, Sweden, representative of street level, urban and rural background. The focus has been on the seldom determined but highly carcinogenic dibenzopyrene isomers (DBPs) dibenzo[a,I]pyrene, dibenzo [a,e]pyrene, dibenzo[a,i]pyrene and dibenzo[a,h]pyrene. PAHs with 3 rings were found to be mainly associated with the vapor phase (>90%) whereas PAHs with 5-6 rings were mostly associated with particulate matter (>92%) and the 4-ringed PAHs partitioned between the two phases. PAH abundance was determined to be in the order street level > urban background > rural background with the PM10 street level 2010 mean of benzo[a]pyrene (B[a]P) reaching 0.24 ng/m(3), well below the EU annual limit value of 1 ng/m(3). In addition, higher PAH concentrations were found in the sub-micron particle fraction (PM1) as compared to the super -micron fraction (PM1-10) with the abundance in PM1 varying between 57 and 86% of the total PAHs. The B[a]P equivalent concentrations derived for DB[a,l]P and total DBPs exceeded 1-2 and 2-4 times, respectively, that of B[a]P at the four sampling sites; therefore underestimation of the cancer risk posed by PAHs in air could be made if the DBPs were not considered in risk assessment using the toxic equivalency approach, whilst the high correlation (p < 0.001) found in the relative concentrations supports the use of B[a]P as a marker substance for assessment of the carcinogenic risk associated to PAHs. However, the big difference in concentration ratios of B[a]P and the DBPs between the present study and some literature data calls for further research to evaluate the temporal and spatial invariance of the B[a]P/DBP ratios.

Keywords
Ambient air, Particulate matter, PAH, Benzo[a]pyrene, Benzo[a]pyrene equivalence, Dibenzo[a, l]pyrene, Toxicity
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-133369 (URN)10.1016/j.atmosenv.2016.06.007 (DOI)000380083200033 ()
Available from: 2016-09-12 Created: 2016-09-06 Last updated: 2018-09-13Bibliographically approved

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